Dioxane derivatives, liquid-crystal compositions containing the same, and liquid-crystal display devices made by using the same

ABSTRACT

The present invention provides liquid crystalline compounds having a high voltage holding ratio and a remarkably high Δε value, electric and chemical stability, and having good compatibility with known liquid crystalline compounds, liquid crystal compositions containing the compound, and liquid crystal display devices constituted by using the compounds. 
     The liquid crystalline compounds of the present invention are particular dioxane derivatives represented by general formula (1). Further, the present invention relates to liquid crystal compositions characterized in that the compositions comprise at least one of the derivatives, and liquid crystal display devices constituted by using the compositions.

This application is a 371 of PCT/SP 97/02257, filed Jun. 30, 1997.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to liquid crystalline compounds effectiveas components of liquid crystal compositions, particularly, dioxanederivatives preferably used as liquid crystal compositions for TFT,liquid crystal compositions containing them, and liquid crystal displaydevices constituted by using these derivatives.

2. Description of the Prior Art

Liquid crystal display devices are obtained by using liquid crystalmaterials having properties of optical anisotropy and dielectricanisotropy. The display modes are twist nematic (TN) mode, dinamicscattering (DS) mode, guest-host (G.H) mode, deformation of alignedphases (DAP) mode, super twist nematic (STN) mode and the like. Theproperties of liquid crystal materials are different in each mode.Lately, in particular, liquid crystal devices having high displayquality are demanded. In response to the demand, a display device of anactive matrix mode represented by a thin film transistor (TFT) mode havebeen used increasingly.

The liquid crystalline compounds used for any display devices should bestable to moisture, air, heat, light and the like. These compounds alsoshould have a liquid crystal phase over a wide range of temperaturesaround room temperature, and have low viscosity, good compatibility tothe other liquid crystalline compounds and liquid crystal compositions,a high dielectric anisotropy value (Δε), and proper optical anisotropy(Δn). These compounds should be stable chemically and electrically.Particularly, the display device of the active matrix mode representedby the TFT mode requires a high voltage holding ratio. However, thereare no materials satisfying these conditions, so that liquid crystalcompositions, which are obtained by mixing several kinds of liquidcrystalline compounds or liquid crystalline compounds, are used underexisting circumstances.

Lately, low voltage driving is demanded to the liquid crystal device ofthe TFT mode. In response to the demand, liquid crystalline compoundsand liquid crystal compositions, which have Δε higher than that of theliquid crystal materials used for conventional liquid crystal displaydevices of the TFT mode, are required. As a result, liquid crystalmaterials having a high voltage holding ratio and high Δε are activelydeveloped. Hitherto, it has been generally known that liquid crystalmaterials of fluorine types show a high voltage holding ratio, andJapanese Patent Publication No. 01-04496 discloses the followingcompound (10).

Since the above compound (10) has a voltage holding ratio higher thanthat of a liquid crystalline compound having a cyano group, it is mainlyused as a component of the liquid crystal composition for TFT. However,extrapolated Δε of compound (10) (extrapolated Δε means that it iscalculated from the value of Δε of the composition, dissolving thecompounds in a mother liquid crystal having a nematic phase, the valueof Δε of the mother liquid crystal and the mixture ratio, and the Δεdescribed hereinafter shows the extrapolated Δε) is small as 8.5. Thecompound can not be used as liquid crystal materials for low voltagedriving, which is represented by 2.5 V driving and demanded in practice.

As a compound having Δε higher than that of compound (10), JapanesePatent Laid-Open Publication No. 02-233626 discloses the trifluorophenylcompound (11) represented by the following formula:

Although Δε of compound (11) is 11.0 and higher than that of compound(10), the value is still too small to satisfy the demand of lowervoltage like the above described value.

Japanese Patent Laid-Open Publication No. 04-506361 disclosestrifluoromethylphenyl derivative (12) and trifluoromethoxyphenylderivative (13).

However, Δε of these compounds can not satisfy the demand of lowervoltage in the market like compounds (10) and (11). (For example, Δε ofcompound (13) is about 5 (IDY (Televigakugihou) 95).

As a compound having higher Δε, Japanese Patent Laid-Open PublicationNo. 02-233626 discloses a dioxane derivative represented by thefollowing formula (14):

Although Δε of the compound is high 15.7, it is impossible to lower thedriving voltage into a necessary level. Moreover, the voltage holdingratio is smaller than that of liquid crystalline compounds of fluorictypes not having a dioxane ring, so that the compound can not becontained in the materials for a liquid crystal display devicesdemanding higher voltage holding ratio As an example, the voltageholding ratio of compound (11) is 98% at a temperature of 25° C. and 96%at 100° C., while that of compound (14) is 98% at 25° C. and 92% at 100°C.

Accordingly, liquid crystalline compounds and liquid crystallinecompounds having both higher Δε and higher voltage ratio have beendesired eagerly.

The inventors of the present invention has studied earnestly to find aliquid crystalline compound most suitable for liquid crystal materialsfor the TFT low voltage driving represented by 2.5V driving, and theyhave found that the liquid crystalline compound, in which a Sp3 carbonis bound to the 2-position of a 1,3-dioxane-2,5-diyl group, and themolecular end has an electron-attracting group of a fluorine or chlorinetype, has specifically high Δε and high voltage holding ratio.

DISCLOSURE OF INVENTION

The object of the present invention is to provide a liquid crystallinecompound having a remarkably high Δε value and high voltage holdingratio, and having good compatibility with known liquid crystallinecompounds, a liquid crystal composition containing the compound, andliquid crystal display device constituted by using the compound.

The present inventors have earnestly studied to accomplish the object,and have found the present invention. Namely, the present invention isas follows:

(1) A dioxane derivative represented by general formula (1):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom,

n1 and n2, each independently, are an integer of 0-2,

n1+n2 ≦2,

Q₁ and Q₂, each independently, are a hydrogen atom, fluorine atom orchlorine atom,

A represents (a), (b) or (c),

ring A0 and A1 represent a 1,4-cyclohexylene group or a 1,4-phenylenegroup, in which 1 or more hydrogen atoms may be replaced by a fluorineatom or a chlorine atom, and one or two carbon atoms may be replaced bya silicon atom in the 1,4-cyclohexylene in A, ring A0 and ring A1,

Za and Zb, each independently, represent a single bond, —CH₂CH₂—,—CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—,

Y represents a hydrogen atom, a halogen atom, or a halogenated alkylgroup of 1-5 carbon atoms, in which one or more not-adjacent methylenegroups may be replaced by an oxygen atom or a sulfur group, in the caseof n1=0 and n2=1, and A is (b) and ring A1 is 1,4-phenylene, and Za andZb are a single bond, or in the case of n1=n2=0 and A is (a) and Zb is asingle bond, at least one of Q1 and Q2 represents a fluorine atom or achlorine atom; in the case of Y is a fluorine atom or a chlorine atom,Q1 and Q2, each independently, represent a fluorine atom or a chlorineatom.

Further, each element constituting the compound may be replaced by itsisotope.

(2) A dioxane derivative according to (1), wherein n1=n2=0, Za is asingle bond, and A=(b).

(3) A dioxane derivative according to (1), wherein n1=n2=0, Za is asingle bond, and A=(a).

(4) A dioxane derivative according to (1), wherein n1+n2=1, and A=(b).

(5) A dioxane derivative according to (1), wherein n1+n2=1, and A=(a).

(6) A dioxane derivative according to (1), wherein n1+n2=2, and A=(b).

(7) A dioxane derivative according to (1), wherein in the case of A=(c),or Zb is —CH₂CH₂CH₂CH₂—, or n1 is not 0, Za is —CH₂CH₂CH₂CH₂—.

(8) A dioxane derivative according to (1), wherein Q1 and Q2 both are afluorine atom.

(9) A liquid crystal composition comprising at least one dioxanederivative according to any one of (1) to (8).

(10) A liquid crystal composition comprising at least one dioxanederivative according to any one of (1) to (8) as the first component,and at least one compound selected from the compound group comprisingcompounds represented by general formulas (2), (3) and (4) as the secondcomponent,

wherein R₃ is an alkyl group of 1-10 carbon atoms, in the alkyl group,at least one not-adjacent methylene group may be replaced by an oxygenatom or —CH═CH—, and any hydrogen atom may be replaced by a fluorineatom, Y₁ represents a fluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃,CF₂H, CFH₂, OCF₂CF₂H or OCF₂CFHCF₃, L₁ and L₂, each independently,represent a hydrogen atom or a fluorine atom, Z₁ and Z₂, eachindependently, —CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —COO—, —CF₂O—, —OCF_(2—),—CH═CH— or a single bond, ring B represents trans-1,4-cyclohexylene,1,3-dioxane-2,5-diyl or 1,4-phenylene, wherein the hydrogen atom may bereplaced by a fluorine atom, ring C represents trans-1,4-cyclohexyleneor 1,4-phenylene, wherein the hydrogen atom may be replaced by afluorine atom, and each element constituting the compound in eachformula may be replaced by its isotope.

(11) A liquid crystal composition comprising at least one dioxanederivative according to any one of (1) to (8) as the first component,and at least one compound selected from the compound group comprisingcompounds represented by general formulas (5) and (6) as the secondcomponent,

wherein R₄ and R₅, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, Y₂ represents —CN or —C≡C—CN,ring E represents trans-1,4-cyclohexylene, 1,4-phenylene,1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl, ring G representstrans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene, whereinthe hydrogen atom may be replaced by a fluorine atom, ring H representstrans-1,4-cyclohexylene or 1,4-phenylene, Z₃ represents —CH₂CH₂—, —COO—or a single bond, L₃, L₄ and L₅, each independently, represent ahydrogen atom or a fluorine atom, b, c and d, each independently, are 0or 1, and each element constituting the compound in each formula may bereplaced by its isotope.

(12) A liquid crystal composition comprising at least one dioxanederivative according to any one of (1) to (8) as the first component,and at least one compound selected from the compound group comprisingcompounds represented by the said general formulas (2), (3) and (4) asthe second component, and at least one compound selected from thecompound group comprising compounds represented by general formulas (7),(8) and (9) as the third component,

wherein R₆ and R₇, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, I, J and K, each independently,represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene,wherein the hydrogen atom may be replaced by a fluorine atom, Z₄ and Z₅,each independently, represent —C≡C—, —COO—, —CH₂C₂—, —CH═CH— or a singlebond, and each element constituting the compound in each formula may bereplaced by its isotope

(13) A liquid crystal composition comprising at least one dioxanederivative according to any one of (1) to (8) as the first component,and at least one compound selected from the compound group comprisingcompounds represented by the said general formulas (5) and (6) as thesecond component, and at least one compound selected from the compoundgroup comprising compounds represented by the said general formulas (7),(8) and (9) as the third component.

(14) A liquid crystal composition comprising at least one dioxanederivative according to any one of (1) to (8) as the first component,and at least one compound selected from the compound group comprisingcompounds represented by the said general formulas (2), (3) and (4) as apart of the second component, and at least one compound selected fromthe compound group comprising compounds represented by the said generalformulas (5) and (6) as another part of the second component, and atleast one compound selected from the compound group comprising compoundsrepresented by the said general formulas (7), (8) and (9) as the thirdcomponent.

(15) A liquid crystal composition according to any one of (9) to (14),wherein the liquid crystal composition further contains an opticalactive compound.

(16) A liquid crystal device constituted by a using liquid crystalcomposition according to any one of (9) to (14).

(17) A liquid crystal display device constituted by using the liquidcrystal composition according to (15).

The compound represented by general formula (1) is a liquid crystallinecompound having 3 rings to 5 rings including a dioxane ring, 2-positionof the dioxane ring is bound to the Sp3 carbon, and the compound has afluorine or chlorine electrophilic group at the molecular end. By suchconstitution, the compound has high voltage holding ratio andspecifically high Δε.

For example, although compound (No. 21) of the present invention has thesame alkyl chain and substituent group of the end benzene ring as thoseof compound (14), the former has specifically high Δε and high voltageholding ratio as described below. The Δε of compound (14) is 15.7, whilethe Δε of compound (No. 21) of the present invention is 23.7. Thevoltage holding ratio of compound (14) is 98% at 25° C. and 92% at 100°C., while that of compound (No. 21) is 98% at 25° C. and 94% at 100° C.

Considering the dipole of each part constitution of the molecule and theangle formed between the dipole and the main axe of moment of inertia,an ordinary person skill in the art may expect that compound (14) andcompound (No. 21) of the present invention have the same degree of Δε.However, the Δε of compound (No. 21) of the present invention is 50%higher than that of compound (14). The fact is unexpected surprisingcharacteristics.

Moreover, the following is an example of the compound of the presentinvention having specifically high Δε.

For example, the Δε of compound (11) is 11.0, while the Δε of compounds(15) and (16) having ethylene as a bonding group are 9.7 which isgenerally less than the former.

Compound (No. 98) of the present invention is obtained by introducing anethylene group as a bonding group to 2-position of the dioxane ring ofcompound (17). The Δε of compound (17) is 25.7, while that of compound(No. 98) is 28.3 higher than that of compound (17) surprisingly.

Such effects are shown only by the liquid crystalline compound havingSp3 carbon bound to 2-position of the dioxane ring and an electrophilicgroup of a fluorine or chlorine at the molecular end. Hitherto, theliquid crystalline compounds having a dioxane ring as shown in thefollowing are disclosed in Japanese Patent Laid-Open Publication Nos.4-503678 and 4-501272.

From a form, the compound of the present invention is included in a partof the said prior arts However, the description of the compound of thepresent invention is not practically found in the specification of theseprior arts. Further, there is no description that the above-mentionedexcellent properties, namely, specifically high Δε and high voltageholding ratio can be foreknown, and the physical values of the saidcompounds are not shown.

US005494606A describes about the dioxane derivative replaced by ahalogen atom at the end of an alkyl group, but excellent properties ofthe compound of the present invention can not be foreknown.

The compound represented by general formula (1), which has a Sp3 carbonbound to 2-position of the dioxane ring and a fulorine or chlorineelectrophilic group at the molecular end, has a high voltage holdingratio and specifically high Δε. The liquid crystal composition preparedby using the compound represented by general formula (1) of the presentinvention has high Δε and high voltage holding ratio, and it is usefulfor lowering the driving voltage of the liquid crystal display device ofthe TFT type.

It has been mentioned that the compounds of the present inventionrepresented by general formula (1) show a high voltage holding ratio anda specifically high Δε, and the compounds of the present invention aredescribed in detail in the following. Although the compound replaced theelement constituting the compound by the isotope is not described in thefollowing, such a compound has the same properties as those of thefollowing compounds.

R represents an alkyl group of 1-20 carbon atoms or a hydrogen atom, andthe alkyl group of preferably 1-7 carbon atoms, more preferably 2-5carbon atoms, is balanced between the viscosity and the temperatureregion of the liquid crystal phase, more preferably, 2-5 carbon atoms.

Bonding groups Za and Zb, each independently, is a single bond,—CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂O—, —OCH₂—, —COO— or —CF₂O—, and thefollowing shows each characteristic.

The compound, whose bonding groups Za and Zb are both single bonds,shows a relative high transpalent point, low viscosity, goodcompatibility to other liquid crystalline compounds or liquid crystalcompositions, and chemical and electrical stability. When one of bondinggroups Za and Zb is a single bond, and the other bond is —CH₂CH₂—, incomparison with the compound having single bonds, the compound showsless viscosity and better compatibility. When at least one of bondinggroups Za and Zb is —CH₂CH₂CH₂CH₂—, in comparison with the compoundhaving a single bond and —CH₂CH₂, the compound shows less viscosity andbetter compatibility. When at least one of bonding groups Za and Zb is—COO—, in comparison with the compounds having the said 5 kinds of otherbonding groups, the compound shows less chemical and physical stabilityand higher Δε. When at least one of bonding groups Za and Zb is —CF₂O—,the compound shows low viscosity and better chemical and physicalstability.

Preferable constitution of end-substituting group Y and characteristicsof the compound having the group are then shown. When Y is fluorine, thecompound has relative high Δε and low viscosity, and good compatibilitywith the other liquid crystalline compounds or liquid crystalcompositions When Y is CF₃, the compound shows high Δε. When Y is OCF₃,or OCF₂H, the compound shows low viscosity. When Y is Cl, —OCF₂CF₂H, or—OCF₂CFHCF₃, the compound has high Δn and a high clearing point. When Yis —OCH₂CF₂H, —OCH₂CF₃ or —OCFHCF₃, the compound has a high clearingpoint, and relative low viscosity. These substituting groups each havethe said characteristics, and very useful. Further, as the othersubstituting groups, Y is preferably —CF₂H, —CF₂Cl, —CH₂CF₃, —CH₂CH₂F,—CH₂CH₂CH₂F, —CH₂CH₂CH₂CH₂F, —OCFH₂, —OCF₂Cl, —OCF₂CF₃, or —OCF₂CF₂CF₃.

The compound of the present invention may have fluorine orchlorine-replaced phenylene groups. The compound having more fluorine orchlorine-replaced groups at lateral positions of the phenylene group hashigher Δε. On the other hand, the compound having less-replaced groupshas a higher clearing point and lower viscosity.

The compounds of the present invention having 1-sila-1,4-cyclohexylenegroup and 4-sila-1,4-cyclohexylene group are better compatibility withthe other liquid crystalline compounds and liquid crystal compositionsat a low temperature than that of the compound having 1,4-cyclohexylenegroup.

The compounds of the present invention have high voltage holding ratio,and have the characteristics aforesaid. Moreover, the compoundsrepresented by general formulas (1-A)-(1-S) have more preferablecharacteristics.

The compound represented by formula (1-A), is that, in general formula(1), n1 and n2 both are 0, Za and Zb both are a single bond, A is (b).

The compound represented by formula (1-B), is that, in general formula(1), n1 and n2 both are 0, Za and Zb both are a single bond, A is (a).

The compound represented by formula (1-C), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is l,4-cyclohexylene, Za and Zb both area single bond, and A is (b)

The compound represented by formula (1-D), is that, in general formula(1), n1 and n2 both are 0, Za is a single bond, Zb is —CH₂CH₂—, A is(a).

The compound represented by formula (1-E), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is replaced or not replaced1,4-phenylene, Za and Zb both are a single bond, and A is (b).

The compound represented by formula (1-F), wherein Zc₂ is a single bond,is that, in general formula (1), n1 is 0, n2 is 1, ring A1 is1,4-cyclohexylene, Za is a single bond, and A is (a).

The compound represented by formula (1-F), wherein Zc₂ is —CH₂CH₂—, isthat, in general formula (1), n1 is 0, n2 is 2, ring A1 is1,4-cyclohexylene, Za is a single bond, and A is (b).

The compound represented by formula (1-G), wherein Zc₂ is a single bond,is that, in general formula (1), n1 is 1, n2 is 0, ring A0 is1,4-cyclohexylene, and A is (a).

The compound represented by formula (1-G), wherein Zc₂ is —CH₂CH₂—, isthat, in general formula (1), n1 and n2 both are 1, ring A0 and A1 bothare 1,4-cyclohexylene, and A is (b).

The compound represented by formula (1-H), is that, in general formula(1), n1 is 2, n2 is 0, ring A0 is 1,4-cyclohexylene, Za and Zb both area single bond, and A is (b).

The compound represented by formula (1-I), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is replaced or not replaced1,4-phenylene, Za and Zb both are a single bond, and A is (a).

The compound represented by formula (1-J), is that, in general formula(1), n1 and n2 both are 1, ring A0 is 1,4-phenylene, ring A1 is replacedor not replaced 1,4-phenylene, Za and Zb both are a single bond, and Ais (b).

The compound represented by formula (1-K), is that, in general formula(1), n1 is 0, n2 is 2, ring A1 is replaced or not replaced1,4-phenylene, Za and Zb both are a single bond, and A is (b).

The compound represented by formula (1-L), is that, in general formula(1), n1 and n2 both are 0, Za and Zb both are a single bond, and A is(c).

The compound represented by formula (1-M), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is 1,4-cyclohexylene, Za and Zb both area single bond, and A is (c).

The compound represented by formula (1-N), is that, in general formula(1), n1 and n2 both are 0, Za is a single bond, Zb is —CH₂CH₂CH₂CH₂—,and A is (a).

The compound represented by formula (1-O), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is replaced or not replaced1,4-phenylene, Za and Zb both are a single bond, and A is (c).

The compound represented by formula (1-P), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is replaced or not replaced1,4-phenylene, Za is a single bond, Zb is —COO— or —CF₂O—, and A is (b).

The compound represented by formula (1-Q), is that, in general formula(1), n1 is 0, n2 is 1, ring A1 is replaced or not replaced1,4-phenylene, Za is a single bond, Zb is —COO— or —CF₂O, and A is (a).

The compound represented by formula (1-R), is that, in general formula(1), n1 is 1, n2 is 0, ring A0 is replaced or not replaced1,4-phenylene, Za and Zb both are a single bond, and A is (a).

The compound represented by formula (1-S), is that, in general formula(1), n1 and n2 both are 0, Za is a single bond, Zb is —COO— or CF₂O, Ais (a).

However, R, Q₁, Q₂ and Y show the same meaning as described above, Q3and Q4, each independently, represent a hydrogen atom or a fluorineatom, Zc₁-Zc₃ each represent single bond or —CH₂CH₂—, Zd represents—CF₂O— or —COO—.

Preferable compounds represented by general formulas (1-A)-(1-S) havethe following characteristics. Generally speaking, the voltage holdingratio of the compounds represented by general formula (1-O), (1-P) and(1-S), wherein Zd is —COO—, is less than that of the other compounds ofthe present invention, but it is higher than that of conventionalcompounds having a benzene ring connected to 2-position of a dioxanering and having —COO—. The other compound of the present invention allsimilarly have high voltage holding ratio. The compounds of the presentinvention can be driven at low voltage because these compounds havespecifically high Δε.

Characteristics exclusive of those of voltage holding ratio and Δε aredescribed in the following.

The compound represented by general formula (1-A) has very low viscosityand very good compatibility. The compound is useful to liquid crystalmaterials for rapid response and components constituting liquid crystalmaterials which can display at a low temperature.

The compound represented by general formula (1-B) has a high clearingpoint and low viscosity.

The compound represented by general formula (1-C) and (1-D) has arelatively high clearing point and good compatibility.

The compounds represented by general formulas (1-B)-(l-D) are wellbalanced in a high clearing point, viscosity and compatibility.

The compound represented by general formula (1-E) has relatively lowviscosity and high Δn. By using the compound, it becomes possible toeasily control the An value of a liquid crystal composition to a desiredvalue and drive at low voltage.

Since the compounds represented by formulas (1-F)-(1-H) have a very highclearing point, these are useful for components constituting liquidcrystal materials, which are able to display at a high temperature.

The compounds represented by general formulas (1-I)-(1-K) and (1R) havea high clearing point and high An. Particularly, An of (1-K) is veryhigh. These compounds also are useful for components constituting liquidcrystal materials, which are able to display at a high temperature.

The compounds represented by general formula (1-L)-(1-O) each having abonding group of —CH₂CH₂CH₂CH₂—, have good compatibility.

The compounds represented by general formulas (1-P), (1-Q) and (1-S),wherein Zd is —COO—, have high clearing point and the compounds, whereinZd is —CF₂O—, have low viscosity.

Conventional compounds do not have such high voltage holding ratio andhigh Δε.

The compounds of the present invention have the said merits, it allowsto drive at low voltage in the liquid crystal display elements thatrequire particular high voltage holding ratio.

The compounds of the present invention are preferably used for liquidcrystal compositions for TFT, and they are used for various otherpurposes. For example, there are liquid crystal compositions for TN, aguest-host mode, a liquid crystal display element of a polymerdispersion type, a dynamic scattering mode and STN, ferroelectric liquidcrystal compositions, anti-ferroelectric liquid crystal compositions,and liquid crystal compositions for inplane switching, an OCB mode and aR-OCB mode.

The term of liquid crystalline compound in the present invention means acompound having a liquid crystal phase and non-liquid crystallinecompound which gives no damage to liquid crystal phase by mixing withthe other liquid crystals.

The liquid crystal compositions of the present invention, which have oneor more compounds represented by general formula (1) of 0.1-99.9% byweight, preferably 1-50% by weight and more preferably 3-20% by weight,are preferred to develop good characteristics.

The liquid crystal compositions provided in the present invention areobtained by adding the first component containing at least one compoundrepresented by general formula (1), and mixing the compound selectedfrom the compound group represented by general formulas (2)-(9)according to the object.

As the compounds represented by general formulas (2)-(4), the followingcompounds are preferably exemplified (R₃ and Y₁ show the same meaning asdescribed above).

The compounds represented by general formulas (2)-(4) are usefulcompounds in the case of preparation of liquid crystal compositions forTFT which require high reliability, such as a positive dielectricanisotropy value, good thermal stability and chemical stability, andhigh voltage holding ratio.

The usage of the compounds represented by general formulas (2)-(4), inthe case of preparation of a liquid crystal composition for TFT, iswithin any range of 1-99% by weight, preferably 10-97% by weight, morepreferably 40-95% by weight. Moreover, in this case, the compoundsrepresented by general formulas (7)-(9) may be contained. In the case ofpreparation of liquid crystal compositions for a TN display mode, thecompounds represented by general formulas (2)-(4) also can be used

As the compounds represented by general formulas (5) and (6), whereinR₄, R₅ and Y₂ have the same meaning as described above, the followingcompounds are preferably exemplified.

The compounds represented by general formulas (5) and (6) are used forobtaining a high positive dielectric anisotropy value and low thresholdvoltage. Further, they are used for controlling an optical anisotropyvalue, and expanding the nematic range, for example, to obtain a highclearing point. Moreover, they are used for improving the steepness of atransmission-voltage curve of liquid crystal compositions for a STNdisplay mode and a TN display mode.

The compounds represented by general formulas (5) and (6) areparticularly useful for preparing liquid crystal composition for a STNdisplay mode and a TN display mode.

The usage of the compound represented by general formulas (5) and (6) isincreased, then, the threshold voltage of the liquid crystalcomposition, and the viscosity is increased Accordingly, in low voltagedriving, it is advantageous to use in large quantities so far as theviscosity of the liquid crystal composition satisfy the desiredcharacteristic value. The usage of the compound represented by generalformulas (5) and (6), for preparing the liquid crystal composition ofthe STN display mode or the TN display mode, it is able to use in therange of 0.1-99.9% by weight, preferably 10-97% by weight, morepreferably 40-95% by weight.

As the compounds represented by general formulas (7)-(9), wherein R₆ andR₇ represents the same meaning as described above, the followingcompounds are preferred.

The absolute value of the dielectric anisotropy value is small in thecompounds represented by general formulas (7)-(9), and almost zero. Thecompounds represented by general formula (7) are used to control theviscosity or optical anisotropy value of compositions. The compoundsrepresented by general formulas (8) and (9) are used for spreading thenematic range to elevate the clearing point and the like and forcontrolling the optical anisotropy value of compositions.

When the usage of the compounds represented by general formulas (7)-(9)is increased, the threshold voltage becomes high, but the viscositybecomes low. Accordingly, so long as the threshold voltage of the liquidcrystal compositions satisfies the necessary value, the usage in largequantities is preferred The usage of the compounds represented bygeneral formulas (7)-(9) is less than 40% by weight in the preparationof liquid crystal compositions for the TFT display mode, and morepreferably less than 35% by weight. Further, in the preparation ofliquid crystal compositions for the STN display mode or the TN displaymode, the usage is less than 70% by weight and more preferably less than60% by weight.

Moreover, in the present invention, except special cases such as liquidcrystal compositions for a OCB (Optically Compensated Birefringence)mode, generally, for inducing a spiral configuration of the liquidcrystal compositions to control the necessary twist angle and to inhibitthe reverse twist, an optically active compound is added. In the liquidcrystal compositions of the present invention, although any well-knownoptically active compounds can be used, preferably the followingoptically active compounds represented by formulas (OP-1)-(Op-8) can beexemplified.

The twist pitch of the liquid crystal compositions of the presentinvention is generally controlled by adding the said optically activecompounds. The twist pitch is preferably adjusted to 40-200 μm in theliquid crystal compositions for TFT or TN. In the liquid crystalcompositions for STN, 6-20 μm are preferred. In addition, in a bistableTN mode, 1.5-4 μm is preferred. Moreover, to control the temperaturedependency of the pitch, two or more optically active compounds may beadded.

The liquid crystal compositions of the present invention can be producedby conventional methods. In general, the compositions are obtained bydissolving several kinds of components each other at a high temperature.

Further, the liquid crystal compositions of the present invention can beused as those of the guest-host (GH) mode by adding dichroic dye such asa merocyanin type, a styryl type, an azo type, an azomethyne type, anazoxy type, a quinophthalon type, an anthraquinone type, and tetrazinetype. Otherwise, the compositions can be used for NCAP prepared bymicro-capsulation of a nematic liquid crystal or for a polymerdispersion liquid crystal display PDLCD) represented by a polymernetwork liquid crystal device (PNLCD). In addition, the compositions canbe used for an electrically controlled birefringence (ECB) mode or adynamic scattering (DS) mode.

Any compounds represented by general formula (1) can be prepared bywell-known method as described in, for example, 4th edition, JikkenKagaku Kouza, (Maruzen), J. Oig. Chem., 42, 1821 (1977), J. Chem. Soc.Perkin Trans. 2, 2041 (1989).

Preferable synthetic process of representative compounds are describedin the following.

The synthetic process of the compound represented by general formula(1-A):

Benzaldehyde derivative (23) is reacted to a reactant solution of ethyldiethylphosphono acetate and sodium hydride to obtain compound (24). Thecompound (24) is hydrogenated by using a catalyst such as palladium, theresulting ester derivative (25) is reduced by using di-isobutyl aluminumhydride (abbreviated by DIBAL, hereinafter) to obtain aldehydederivative (26). This aldehyde derivative (26) and2-alkyl-1,3-propandiol are refluxed under dehydration in the presence ofan acidic catalyst such as para-toluene sulfonic acid (abbreviated byPTS, hereinafter) or acidic ion exchange resin (Amberlyst R) to obtainthe compound represented by general formula (1-A).

The synthetic process of the compound represented by general formula(1-B).

Cyclohexanedion monoethylene ketal (28) is reacted to Grignard reagent(27) to obtain tertiary alcohol (29). The resulting compound isdehydrated and hydrogenated, and then deprotected under acidicconditions to obtain a cyclohexanone derivative (31). To this compound,methoxymethyl triphenylphosphonium chloride is reacted, and thendeprotected under acidic conditions to obtain aldehyde derivative (32).This compound is reacted with 2-alkyl-1,3-propan-diol under acidicconditions to obtain the compound represented by general formula (1-B).

The synthetic process of the compound represented by general formula(1-C):

The compound represented by general formula (1-C) can be obtained byusing the same method as described in the synthetic process of thecompound represented by general formula (1-A) except replacing aldehydederivative (23) by aldehyde derivative (32).

The synthetic process of the compound represented by general formula(1-D):

The compound represented by general formula (1-D) can be obtained byusing the same method as described in the synthetic process of thecompound represented by general formula (1-B) except replacing Grignardreagent (27) by Grignard reagent (34).

The synthetic process of the compound represented by general formula(1-E):

Compound (35) represented by general formula (1-A), wherein Y is ahydrogen atom, is synthesized. Compound (35) is reacted withbutyllithium to obtain a lithio compound, and then reacted with zincchloride, palladium (0) and compound (36) in order, to obtain thecompound represented by general formula (1-E). This process is appliedby the method described in J. Org. Chem., 42, 1821 (1977). Further, themethod described in J. Chem. Soc. Perkin Trans. 2, 2041 (1989) can beapplied.

The synthetic process of the compound represented by general formula(1-L):

The compound represented by general formula (1-L) can be obtained byusing the same method as described in the synthetic process of thecompound represented by general formula (1-A) except replacing aldehydederivative (23) by compound (26).

The synthetic process of the compound represented by general formula(1-M):

The compound represented by general formula (1-M;) can be obtained byusing the same method as described in the synthetic process of thecompound represented by general formula (1-A) except replacing aldehydederivative (23) by compound (33).

The synthetic process of the compound represented by general formula(1-N):

Aldehyde derivative (23) is reacted to a ylide prepared from a base suchas 1,3-dioxane-2-yl ethyltriphenylphosphonium bromide andpotassium-t-butoxide, and the resulting product is hydrogenated, andthen it is deprotected by an add to obtain aldehyde derivative (40). Areduction agent such as sodium boron hydride is reacted to thederivative, the resulting alcohol derivative is brominated withhydrobromic acid or the like to obtain compound (41), and then it isreacted with magnesium to prepare Grignard reagent (42). The compoundrepresented by general formula (1-N) can be obtained by using the samemethod as described in the synthetic process of the compound representedby general formula (1-B) except replacing Grignard reagent (27) byGrignard reagent (42).

The synthetic process of the compound represented by general formula(1-O):

Compound (43) represented by general formula (1-L), wherein Y is ahydrogen atom, is synthesized. The compound represented by generalformula (1-O) can be obtained by using the same method as described inthe synthesis of the compound represented by general formula (1-E)except replacing compound (35) by compound (43).

The synthetic process of the compound represented by general formula(1-P):

Compound (35) is reacted with butyl lithium, the resulting lithiocompound is reacted with carbon dioxide as described in 4th edition,Jikken Kagaku Kouza Maruzen), Vol.22, page 16, and a carboxylic acidderivative (44) is obtained. To this carboxylic acid derivative (44), byusing a method described in the said Jikken Kagaku Kouza, Vol.22, page46, phenol derivative (45) is reacted in the presence of4-dimethylaminopyridine and 1,3-dicyclohexylcarbodiimide (abbreviated asDCC, hereinafter), and ester derivative (46) can be obtained. Thiscompound is represented by general formula (1-P) wherein Zd is —COO—.

As described in Bull. Soc. Chim. Belg., 87, 293 (1978), ester compound(46) is reacted with a Lawesson's reagent, the resulting thionester (47)is reacted with diethylamino sulfur trifluoride (abbreviated as DAST,hereinafter) in methylene chloride or glyme solvent, or as described inJapanese Patent Laid-Open Publication No. 6-263679, it is reacted withtetra-butyl ammonium di-hydrogen tri-fluoride (abbreviated as TBAH2F3,hereinafter) and N-iodo succinimide (abbreviated as NIS hereinafter) inthe presence of mehtylene chloride and 1,2-dichloroethane, anddifluoromethylether (48) can be obtained. The compound is represented bygeneral formula (1-P) wherein Zd is —CF₂O—.

Using a method described in Helv. Chim. Acta., 27, 793 (1944),cyclohexanone-4-carboxylic acid ethyl ester (50) can be synthesized frompentane-1,3,3,5-tetracrboxylic acid tetraethyl ester (49). Otherwise,cyclohexanedione monoethylene ketal is reacted withmethoxymethyltriphenyl phosphonium chloride, and deprotected underacidic conditions, and aldehyde derivative (51) is obtained. Theresulting compound is oxidized by a method described in 4th edition,Jikken Kagaku Kouza, Vol. 22, pages 3-4, to obtain carboxylic acidderivative (52). Then, by a method described in 4th edition, JikkenKagaku Kouza, Vol. 22, pages 44-47, the derivative is reacted to obtainester compound (50). This compound is reacted with methoxy methyltriphenyl phosphonium chloride, and the resulting product is deprotectedunder acidic conditions to obtain aldehyde derivative (53). Exceptreplacing compound (26) by compound (53), using the same method asdescribed in the synthesis of the compound represented by generalformula (1-A), compound (54) can be obtained. From the compound (54),compound (55) is synthesized by using a hydrolysis method under alkalior neutral conditions as described in 4th edition, Jikken Kagaku Kouza,Vol. 22, pages 8-11. And then ester compound (56) can be synthesized bya method described in 4th edition, Jikken Kagaku Kouza, Vol. 22, pages45-47. This compound is represented by general formula (1-S) wherein Zdis —COO—.

By using the same method as described in the synthesis of compound (48)except replacing compound (46) by compound (56), the compoundrepresented by general formula (1-S), wherein Zd is —CF₂O—, can beobtained.

The compounds having four rings represented by general formulas(1-F)-(1-K and (1-Q), and (1-R) can be easily produced by using theabove synthetic method of the tricyclic compounds.

The compounds having a 1-sila-1,4-cyclohexylene group and a4-sila-4-cyclohexylene group in the present invention can be prepared byapplying the method described in Japanese Patent Laid-open Publication7-70148.

As examples of the liquid crystal compositions containing the compoundsof the present invention, the following composition examples Compositionexamples 1-49) can be represented In each composition example, eachcompound is represented by a symbol based on the abbreviation methoddescribed in the following Table 1, and groups represented in eachcolumn of left end groups, bonding groups, ring structure, and right endgroup correspond to those in the column of symbolized examples. As anexample, in the following constitutional formula, when hydrogen atoms oftrans-1,4-cyclohexylene and trans, trans-bicyclohexane-4,4′-diyl arereplaced at the positions of J₁, J₂ and J₃, the symbol is read as H[1D,2D, 3D], when the hydrogen atoms are replaced at the positions of J₅, J₆and J₇, the symbol is read as H[5D, 6D, 7D], and the numbers in [ ] showthe positions replaced by heavy hydrogen atoms.

The compound Nos. are the same as in those of the examples described inthe following, and the content of the compounds means % by weight,except special mention.

The data of characteristics in using examples are shown by T_(N1)(nematic-isotropy liquid transition temperature or clearing point), η(viscosity: measured temperature 20.0° C.), Δn(optical anisotropy:measured temperature 25.0° C., Δε1(dielectric anisotropy: measuredtemperature 25.0° C.) and V_(th) (threshold voltage: measuredtemperature 25.0° C.).

TABLE 1 Representation of compounds by using symbolsRA₁Z₁—Z_(n)A_(n)X 1) Left 3) Bonding end groups R— Symbols groups—Z₁—, —Z_(n)— Symbols C_(n)H_(2n+1)— n- —C₂H₄— 2C_(n)H_(2n+1)OC_(m)H_(2m)— nOm- —COO— E —CF₂O— CF2O 2) Ring Structure 4)Right A₁, A_(n) Symbols end groups —X Symbols

B —F —F

B(F) —Cl —CL

B(F,F) —OCF₃ —OCF3

H —C_(n)H_(2n+1) -n

Py

D

Ch 5) Symbolized examples Example 1 3-H2B(F,F)B(F)—F

Example 2 3-HB(F)TB-2

Example 3 IV2-BEB(F,F)—C

Composition Example 1

3-DHB(F,F)—F 3.0% (Compound No. 21) 3-D2B(F,F)B(F)—OCF3 3.0% (CompoundNo. 98) 1V2-BEB(F,F)—C 5.0% 3-HB—C 25.0% 1-BTB-3 5.0% 2-BTB-1 10.0%3-HH-4 11.0% 3-HHB-1 5.0% 3-HHB-3 9.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0%3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0% Op-4 0.8 part T_(n1) =83.5(° C.) η = 17.5 (mPa · s) Δn = 0.159 Δε1 = 8.1 V_(th) = 1.98(V) P =11 μm

Composition Example 2

3-D2B—CF3 2.0% (Compound No. 11) 3-D4B—CF3 2.0% (Compound No. 261)3-DHB(F,F)B(F)—CL 4.0% (Compound No. 175) V2-HB—C 10.0% 1V2-HB—C 10.0%3-HB—C 11.0% 3-H[1D,2D,3D]B—C 9.0% 3-HB(F)—C 5.0% 2-BTB-1 2.0% 3-HH-48.0% 3-HH—VFF 6.0% 2-H[1D,2D,3D]HB—C 3.0% 3-HHB—C 6.0% 3-HB(F)TB-2 8.0%3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4.0% T_(n1) = 89.2(° C.) η =19.0 (mPa · s) Δn = 0.151 Δε1 = 8.8 V_(th) = 1.98(V)

Composition Example 3

3-DHB(F)—OCF3 5.0% (Compound No. 22) 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C15.0% 4O1-BEB(F)—C 13.0% 5O1-BEB(F)—C 10.0% 2-HHB(F)—C 15.0% 3-HHB(F)—C15.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 6.0%3-HHB—O1 4.0% T_(n1) = 92.6(° C.) η = 86.5 (mPa · s) Δn = 0.148 Δε1 =31.2 V_(th) = 0.86(V)

Composition Example 4

3-DHB(F,F)—F 3.0% (Compound No. 21) 3-DHB(F)—OCF3 3.0% (Compound No. 22)5-PyB—F 4.0% 3-PyB(F)—F 4.0% 2-BB—C 5.0% 4-BB—C 4.0% 5-BB—C 5.0% 2-PyB-22.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB—O5 3.0% 6-PyB—O6 3.0% 6-PyB—O7 3.0%3-PyBB—F 6.0% 4-PyBB—F 6.0% 5-PyBB—F 3.0% 3-HHB-1 6.0% 3-HHB-3 8.0%2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-35.0% 3-H2BTB-4 5.0% T_(n1) = 91.7(° C.) η = 35.1 (mPa · s) Δn = 0.195Δε1 = 7.6 V_(th) = 2.19(V)

Composition Example 5

3-D2B(F,F)B(F)—OCF3 5.0% (Compound No. 98) 3-D2B—CF3 3.0% (Compound No.11) 3-D4B—CF3 2.0% (Compound No. 261) 3-DB—C 8.0% 4-DB—C 5.0% 2-BEB—C12.0% 3-BEB—C 4.0% 3-PyB(F)—F 3.0% 3-HEB—O4 8.0% 4-HEB—O2 6.0% 5-HEB—O16.0% 3-HEB—O2 5.0% 5-HEB—O2 4.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 1O—BEB-2 4.0%3-HHB-1 6.0% 3-HHEBB—C 3.0% 3-HBEBB—C 3.0% 5-HBEBB—C 3.0% T_(n1) =67.4(° C.) η = 39.9 (mPa · s) Δn = 0.119 Δε1 = 11.1 V_(th) = 1.37(V)

Composition Example 6

3-DHB(F,F)—F 3.0% (Compound No. 21) 3-D2B(F,F)B(F)—OCF3 3.0% (CompoundNo. 98) 3-DHB(F)—OCF3 3.0% (Compound No. 22) 3-HB—C 13.0% 7-HB—C 3.0%1O1-HB—C 6.0% 3-HB(F)—C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0%1O1-HH-3 7.0% 2-BTB—O1 7.0% 3-HHB-1 7.0% 3-HHB—F 4.0% 3-HHB—O1 4.0%3-HHB-3 8.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0%3-PyBB-2 3.0% T_(n1) = 79.6(° C.) η = 21.1 (mPa · s) Δn = 0.137 Δε1 =8.5 V_(th) = 1.68(V)

Composition Example 7

3-D2B—CF3 4.0% (Compound No. 11) 3-DHB(F)—OCF3 5.0% (Compound No. 22)2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 10.0% 1V2-BEB(F,F)—C 10.0% 3-HH—EMe 10.0%3-HB—O2 18.0% 7-HEB—F 2.0% 3-HHEB—F 2.0% 5-HHEB—F 2.0% 3-HBEB—F 4.0%2O1-HBEB(F)—C 2.0% 3-HB(F)EB(F)—C 2.0% 3-HBEB(F,F)—C 2.0% 3-HHB—F 4.0%3-HHB—O1 4.0% 3-HHB-3 10.0% 3-HEBEB—F 2.0% 3-HEBEB-1 2.0% T_(n1) =74.5(° C.) η = 33.7 (mPa · s) Δn = 0.110 Δε1 = 22.9 V_(th) = 1.01(V)

Composition Example 8

3-DHB(F,F)—F 3.0% (Compound No. 21) 3-DHB(F,F)B(F)—CL 3.0% (Compound No.175) 5-BEB(F)—C 5.0% V—HB—C 11.0% 5-PyB—C 6.0% 4-BB-3 11.0% 3-HH-2V10.0% 5-HH—V 8.0% V—HHB-1 7.0% V2-HHB-1 15.0% 3-HHB-1 9.0% 1V2-HBB-27.0% 3-HHEBH-3 5.0% T_(n1) = 91.0(° C.) η = 19.2 (mPa · s) Δn = 0.116Δε1 = 6.1 V_(th) = 2.19(V)

Composition Example 9

3-D2B—(F,F)B(F)—OCF3 5.0% (Compound No. 98) 3-D2B—CF3 2.0% (Compound No.11) 3-D4B—CF3 3.0% (Compound No. 261) 3-DHB(F,F)B(F)—CL 5.0% (Compoundno. 175) 2O1-BEB(F)—C 5.0% 3O1-BEB(F)—C 8.0% 1V2-BEB(F,F)—C 16.0%3-HB—O2 10.0% 3-HH-4 3.0% 3-HHB—F 3.0% 3-HHB-1 5.0% 3-HHB—O1 4.0%3-HBEB—F 4.0% 3-HHEB—F 7.0% 5-HHEB—F 7.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0%3-HB(F)TB-2 5.0% T_(n1) = 87.5(° C.) η = 41.7 (mPa · s) Δn = 0.133 Δε1 =28.2 V_(th) = 1.02(V)

Composition Example 10

3-D2B—(F,F)B(F)—OCF3 5.0% (Compound No. 98) 3-DHB(F)—OCF3 5.0% (CompoundNo. 22) 2-BEB—C 12.0% 4-BEB—C 6.0% 3-HB—C 22.0% 3-HEB—O4 12.0% 4-HEB—O28.0% 5-HEB—O1 8.0% 3-HEB—O2 6.0% 5-HEB—O2 5.0% 3-HHB-1 7.0% 3-HHB—O14.0% T_(n1) = 61.5(° C.) η = 29.0 (mPa · s) Δn = 0.107 Δε1 = 10.3 V_(th)= 1.32(V)

Composition Example 11

3-D4B—CF3 4.0% (Compound No. 261) 3-DHB(F,F)—B(F)—CL 4.0% (Compound No.175) 2-BEB—C 10.0% 5-BB—C 8.0% 7-BB—C 7.0% 1-BTB-3 7.0% 2-BTB-1 10.0%1O—BEB-2 10.0% 1O—BEB-5 12.0% 2-HHB-1 4.0% 3-HHB—F 4.0% 3-HHB-1 7.0%3-HHB—O1 4.0% 3-HHB-3 9.0% T_(n1) = 64.9(° C.) η = 20.8 (mPa · s) Δn =0.155 Δε1 = 6.9 V_(th) = 1.72(V)

Composition Example 12

3-DHB(F,F)—F 5.0% (Compound No. 21) 3-D2B(F,F)—B(F)—OCF3 5.0% (CompoundNo. 98) 1V2-BEB(F,F)—C 6.0% 3-HB—C 10.0% V2V—HB—C 14.0% V2V—HH-3 19.0%3-HB—O2 4.0% 3-HHB-1 7.0% 3-HHB-3 10.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-34.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% T_(n1) = 92.6(° C.) η= 21.4 (mPa · s) Δn = 0.126 Δε1 = 8.9 V_(th) = 1.97(V)

Composition Example 13

3-D2B(F,F)B(F)—OCF3 5.0% (Compound No. 98) 3-DHB(F)—OCF3 5.0% (CompoundNo. 22) 5-BTB(F)TB-3 10.0% V2-HB—TC 10.0% 3-HB—TC 10.0% 3-HB—C 10.0%5-HB—C 7.0% 5-BB—C 3.0% 2-BTB-1 10.0% 2-BTB—O1 5.0% 3-HH-4 5.0% 3-HHB-311.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB(F)TB-2 3.0% T_(n1) = 89.4(° C.)η = 18.6 (mPa · s) Δn = 0.201 Δε1 = 8.7 V_(th) = 1.81(V)

Composition Example 14

3-DHB(F,F)—F 3.0% (Compound No. 21) 3-D4B—CF3 3.0% (Compound No. 261)3-DHB(F,F)B(F)—CL 3.0% (Compound No. 175) 1V2-BEB(F,F)—C 6.0% 3-HB—C18.0% 2-BTB-1 10.0% 5-HH—VFF 25.0% 1-BHH—VFF 8.0% 1-BHH-2VFF 11.0%3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-HHB-1 4.0% T_(n1) = 77.6(° C.) η = 15.6(mPa · s) Δn = 0.125 Δε1 = 7.9 V_(th) = 1.90(V)

Composition Example 15

3-DHB(F,F)—F 4.0% (Compound No. 21) 3-D2B—CF3 4.0% (Compound No. 11)3-DHB(F)—OCF3 4.0% (Compound No. 22) 3-DHB(F,F)B(F)—CL 4.0% (compoundNo. 175) 2-HB—C 5.0% 3-HB—C 7.0% 3-HB—O2 15.0% 2-BTB-1 3.0% 3-HHB-1 8.0%3-HHB—F 4.0% 3-HHB—O1 5.0% 3-HHB-3 14.0% 3-HHEB—F 4.0% 2-HHB(F)—F 7.0%3-HHB(F)—F 7.0% 3-HHB(F,F)—F 5.0% T_(n1) = 86.6(° C.) η = 23.9 (mPa · s)Δn = 0.092 Δε1 = 6.9 V_(th) = 2.12(V)

Composition Example 16

3-D2B-CF3 5.0% (Compound No.11) 3-D4B-CF3 5.0% (Compound No.261)3-DHB(F, F)-F 10.0% (Compound No.21) 3-D2B(F, F)B(F)-OCF3 10.0%(Compound No.98) 3-DHB(F)-OCF3 10.0% (Compound No.22) 3-DHB(F, F)B(F)-CL5.0% (Compound No.175) 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 12.0% 1V2-BEB(F,F)-C 7.0% 3-HB-O2 10.0% 3-HHB-F 3.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0%5-HHEB-F 7.0% T_(N1) = 57.8(° C.) η = 50.4 (mPa.s) Δn = 0.095 Δ ε 1 =28.9 V_(th) = 0.98(V)

Composition Example 17

3-D2B(F, F)B(F)-OCF3 5.0% (Compound No.98) 3-DHB(F)-OCF3 5.0% (CompoundNo.22) 2-HHB(F)-F 17.0% 3-HHB(F)-F 17.0% 5-HHB(F)-F 16.0% 2-H2HB(F)-F6.0% 3-H2HB(F)-F 5.0% 5-H2HB(F)-F 10.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F 13.0%Op-8 0.3 part T_(N1) = 98.6(° C.) η = 28.3 (mPa.s) Δn = 0.094 Δ ε 1 =6.8 V_(th) = 1.99(V) P = 79 μm

Composition Example 18

3-D2B-CF3 4.0% (Compound No.11) 3-DHB(F)-OCF3 4.0% (Compound No.22)7-HB(F)-F 3.0% 5-H2B(F)-F 3.0% 3-HB-O2 10.0% 3-HH-4 2.0% 3-HH[5D, 6D,7D]-4 3.0% 2-HHB(F)-F 6.0% 3-HHB(F)-F 10.0% 5-HH[5D, 6D, 7D]B(F)-F 10.0%3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0%2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB-1 8.0% 3-HHB-O1 5.0% 3-HHB-34.0% T_(N1) = 88.4(° C.) η = 19.3 (mPa.s) Δn = 0.094 Δ ε 1 = 4.0 V_(th)= 2.50(V)

Composition Example 19

3-D2B-CF3 5.0% (Compound No.11) 3-D4B-CF3 5.0% (Compound No.261)3-DHB(F, F)B(F)-CL 4.0% (Compound No.175) 7-HB(F, F)-F 3.0% 3-HB-O2 7.0%3-HHB(F)-F 10.0% 5-HHB(F)-F 10.0% 2-HBB(F)-F 9.0% 3-HBB(F)-F 9.0%5-HBB(F)-F 16.0% 2-HBB-F 4.0% 3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB(F, F)-F5.0% 5-HBB(F, F)-F 6.0% T_(N1) = 78.8(° C.) η = 24.3 (mPa.s) Δn = 0.111Δ ε 1 = 6.6 V_(th) = 1.90(V)

Composition Example 20

3-D2B(F, F)B(F)-OCF3 5.0% (Compound No.98) 3-DHB(F, F)B(F)-CL 3.0%(Compound No.175) 7-HB(F, F)-F 3.0% 3-H2HB(F, F)-F 12.0% 4-H2HB(F, F)-F10.0% 5-H2HB(F, F)-F 10.0% 3-HHB(F, F)-F 5.0% 4-HHB(F, F)-F 5.0%3-HH2B(F, F)-F 7.0% 5-HH2B(F, F)-F 10.0% 3-HBB(F, F)-F 12.0% 5-HBB(F,F)-F 12.0% 3-HBCF2OB(F, F)-F 6.0% T_(N1) = 71.8(° C.) η = 28.9 (mPa.s)Δn = 0.089 Δ ε 1 = 10.0 V_(th) = 1.46(V)

Composition Example 21

3-D4B-CF3 5.0% (Compound No.261) 3-DHB(F)-OCF3 5.0% (Compound No.22)3-DHB(F, F)B(F)-CL 5.0% (Compound No.175) 7-HB(F, F)-F 5.0% 3-H2HB(F,F)-F 12.0% 4-H2HB(F, F)-F 10.0% 3-HHB(F, F)-F 10.0% 3-HBB(F, F)-F 10.0%3-HHEB(F, F)-F 10.0% 4-HHEB(F, F)-F 3.0% 5-HHEB(F, F)-F 3.0% 2-HBEB(F,F)-F 3.0% 3-HBEB(F, F)-F 5.0% 5-HBEB(F, F)-F 3.0% 3-HDB(F, F)-F 5.0%3-HHBB(F, F)-F 6.0% T_(N1) = 76.6(° C.) η = 36.0 (mPa.s) Δn = 0.088 Δ ε1 = 13.7 V_(th) = 1.26(V)

Composition Example 22

3-D2B-CF3 5.0% (Compound No.11) 3-DHB(F, F)B(F)-CL 5.0% (CompoundNo.175) 3-HB-CL 10.0% 5-HB-CL 4.0% 7-HB-CL 4.0% 1O1-HH-5 5.0% 2-HBB(F)-F3.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F 14.0% 4-HHB-CL 8.0% 5-HHB-CL 3.0%3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 10.0% 5-H2BB(F, F)-F 9.0% 3-HB(F)VB-24.0% 3-HB(F)VB-3 4.0% T_(N1) = 87.4(° C.) η = 21.3 (mPa.s) Δn = 0.126 Δε 1 = 5.9 V_(th) = 2.18(V)

Composition Example 23

3-D2B(F, F)B(F)-OCF3 7.0% (Compound No.98) 3-D2B-CF3 5.0% (CompoundNo.11) 3-D4B-CF3 5.0% (Compound No.261) 3-DHB(F)-OCF3 8.0% (CompoundNo.22) 3-DHB(F, F)B(F)-CL 5.0% (Compound No.175) 3-HHB(F, F)-F 9.0%3-H2HB(F, F)-F 8.0% 4-H2HB(F, F)-F 8.0% 3-HBB(F, F)-F 13.0% 5-HBB(F,F)-F 10.0% 3-H2BB(F, F)-F 10.0% 5-HHBB(F, F)-F 3.0% 5-HHEBB-F 2.0%3-HH2BB(F, F)-F 3.0% 1O1-HBBH-4 4.0% T_(N1) = 82.4(° C.) η = 37.5(mPa.s) Δn = 0.105 Δ ε 1 = 12.2 V_(th) = 1.44(V)

Composition Example 24

3-D2B(F, F)B(F)-OCF3 5.0% (Compound No.98) 5-HB-F 12.0% 6-HB-F 9.0%7-HB-F 7.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 7.0% 4-HHB-OCF3 7.0% 5-HHB-OCF35.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0% 3-HHB(F, F)-OCF3 5.0% 3-HBB(F)-F5.0% 5-HBB(F)-F 10.0% 3-HH2B(F)-F 3.0% 3-HB(F)BH-3 3.0% 5-HBBH-3 3.0%3-HHB(F, F)-OCF2H 4.0% T_(N1) = 84.2(° C.) η = 16.5 (mPa.s) Δn = 0.090 Δε 1 = 5.5 V_(th) = 2.25(V)

Composition Example 25

3-DHB(F)-OCF3 5.0% (Compound No.22) 3-DHB(F, F)B(F)-CL 3.0% (CompoundNo.175) 5-H4HB(F, F)-F 7.0% 5-H4HB-OCF3 7.0% 3-H4HB(F, F)-CF3 8.0%5-H4HB(F, F)-CF3 10.0% 3-HB-CL 6.0% 5-HB-CL 4.0% 2-H2BB(F)-F 5.0%3-H2BB(F)-F 10.0% 5-HVHB(F, F)-F 5.0% 3-HHB-OCF3 5.0% 3-H2HB-OCF3 5.0%V-HHB(F)-F 3-HHB(F)-F 5.0% 5-HHEB-OCF3 2.0% 3-HBEB(F, F)-F 5.0% 5-HH-V2F3.0% T_(N1) = 70.8(° C.) η = 28.1 (mPa.s) Δn = 0.096 Δ ε 1 = 9.5 V_(th)= 1.60(V)

Composition Example 26

3-D2B(F, F)B(F)-OCF3 4.0% (Compound No.98) 3-D4B-CF3 4.0% (CompoundNo.261) 3-DHB(F, F)B(F)-CL 4.0% (Compound No.175) 2-HHB(F)-F 2.0%3-HHB(F)-F 2.0% 5-HHB(F)-F 2.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0%5-HBB(F)-F 4.0% 2-H2BB(F)-F 9.0% 3-H2BB(F)-F 3.0% 3-HBB(F, F)-F 25.0%5-HBB(F, F)-F 19.0% 1O1-HBBH-4 5.0% 1O1-HBBH-5 5.0% T_(N1) = 91.6(° C.)η = 36.5 (mPa.s) Δn = 0.129 Δ ε 1 = 9.0 V_(th) = 1.67(V)

Composition Example 27

3-D2B(F, F)B(F)-OCF3 3.0% (Compound No.98) 3-D2B-CF3 3.0% (CompoundNo.11) 3-DHB(F)-OCF3 3.0% (Compound No.22) 5-HB-CL 8.0% 3-HH-4 7.0%3-HB-O2 20.0% 3-H2HB(F, F)-F 8.0% 3-HHB(F, F)-F 8.0% 3-HBB(F, F)-F 6.0%3-HHB(F)-F 5.0% 5-HHB(F)-F 5.0% 2-H2HB(F)-F 2.0% 3-H2HB(F)-F 1.0%5-H2HB(F)-F 2.0% 3-HHBB(F, F)-F 4.0% 3-HBCF2OB-OCF3 4.0% 5-HBCF2OB(F,F)-CF3 4.0% 3-HHB-1 3.0% 3-HHB-O1 4.0% T_(N1) = 69.5(° C.) η = 18.0(mPa.s) Δn = 0.084 Δ ε 1 = 5.4 V_(th) = 2.03(V)

Composition Example 28

3-D2B(F, F)B(F)-OCF3 5.0% (Compound No.98) 3-BEB(F)-C 8.0% 3-HB-C 8.0%V-HB-C 8.0% 1V-HB-C 8.0% 3-HB-O2 3.0% 3-HH-2V 14.0% 3-HH-2V1 7.0%V2-HHB-1 15.0% 3-HHB-1 5.0% 3-HHEB-F 7.0% 3-H2BTB-2 6.0% 3-H2BTB-3 6.0%T_(N1) = 91.9(° C.) η = 18.7 (mPa.s) Δn = 0.126 Δ ε 1 = 9.6 V_(th) =1.98(V)

Composition Example 29

3-D4B-CF3 4.0% (Compound No.261) 3-DHB(F)-OCF3 5.0% (Compound No.22)3-DHB(F, F)B(F)-CL 3.0% (Compound No.175) 3-H2HB(F, F)-F 7.0% 5-H2HB(F,F)-F 8.0% 3-HHB(F, F)-F 10.0% 3-HH2B(F, F)-F 9.0% 5-HH2B(F, F)-F 9.0%3-HBB(F, F)-F 15.0% 5-HBB(F, F)-F 10.0% 4-HBEB(F, F)-F 2.0% 5-HBEB(F,F)-F 2.0% 3-HHEB(F, F)-F 10.0% 4-HHEB(F, F)-F 3.0% 5-HHEB(F, F)-F 3.0%T_(N1) = 79.3(° C.) η = 33.4 (mPa.s) Δn = 0.090 Δ ε 1 = 12.0 V_(th) =1.65(V)

Composition Example 30

2-DH2B(F)-F 5.0% (Compound No.51) 2-D2BEB-CL 5.0% (Compound No.311)2-HHB(F)-F 17.0% 3-HHB(F)-F 17.0% 5-HHB(F)-F 16.0% 3-H2HB(F)-F 5.0%5-H2HB(F)-F 10.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F 13.0%

Composition Example 31

2-HD2B(F)-CF3 5.0% (Compound No.46) 3-D2B(F)CF2OB(F)-CF3 5.0% (CompoundNo.317) 7-HB(F)-F 5.0% 5-H2B(F)-F 5.0% 3-HB-O2 10.0% 3-HH-4 2.0%3-HH[5D, 6D, 7D]-4 3.0% 3-HHB(F)-F 10.0% 5-HH[5D, 6D, 7D]B(F)-F 10.0%3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0%2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB-1 8.0% 3-HHB-O1 5.0% 3-HHB-34.0%

Composition Example 32

2-DH2B(F)-F 5.0% (Compound No.51) 3-D2HB(CL)-OCF2H 5.0% (Compound No.40)7-HB(F, F)-F 3.0% 3-HB-O2 7.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0%5-HHB(F)-F 10.0% 2-HBB(F)-F 9.0% 3-HBB(F)-F 9.0% 5-HBB(F)-F 16.0%2-HBB-F 4.0% 3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB(F, F)-F 3.0%

Composition Example 33

2-HD2B(F)-CF3 5.0% (Compound No.46) 2-D2BEB-CL 5.0% (Compound No.311)3-D2HB(CL)-OCF2H 5.0% (Compound No.40) 7-HB(F, F)-F 3.0% 3-H2HB(F, F)-F12.0% 4-H2HB(F, F)-F 10.0% 3-HHB(F, F)-F 5.0% 4-HHB(F, F)-F 5.0%3-HH2B(F, F)-F 15.0% 5-HH2B(F, F)-F 10.0% 3-HBB(F, F)-F 12.0% 5-HBB(F,F)-F 7.0% 3-HBCF2OB(F, F)-F 6.0%

Composition Example 34

3-D2B(F)-CF2OB(F)-CF3 5.0% (Compound No.317) 1-HD2B(F)B(F, F)-OCF2CFHCF33.0% (Compound No.236) 7-HB(F, F)-F 5.0% 3-H2HB(F, F)-F 12.0% 4-H2HB(F,F)-F 10.0% 3-HHB(F, F)-F 10.0% 4-HHB(F, F)-F 5.0% 3-HHB(F, F)-F 10.0%3-HHEB(F, F)-F 10.0% 4-HHEB(F, F)-F 3.0% 5-HHEB(F, F)-F 3.0% 2-HBEB(F,F)-F 3.0% 3-HBEB(F, F)-F 5.0% 5-HBEB(F, F)-F 3.0% 3-HDB(F, F)-F 10.0%3-HHBB(F, F)-F 3.0%

Composition Example 35

2-DH2B(F)-F 5.0% (Compound No.51) 3-HB-CL 10.0% 5-HB-CL 4.0% 7-HB-CL4.0% 1O1-HH-5 5.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F 9.0%4-HHB-CL 8.0% 5-HHB-CL 8.0% 3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 10.0%5-H2BB(F, F)-F 9.0% 3-HB(F)VB-2 4.0% 3-HB (F)VB-3 4.0%

Composition Example 36

2-HD2B(F)-CF3 4.0% (Compound No. 46) 1-HD2B(F)B(F, F)-OCF2CFHCF3 3.0%(Compound No. 236) 3-D2B(F, F)B(F)B(F)-OCF2H 3.0% (Compound No. 228)3-HHB(F, F)-F 9.0% 3-H2HB(F, F)-F 8.0% 4-H2HB(F, F)-F 8.0% 5-H2HB(F,F)-F 4.0% 3-HBB(F, F)-F 19.0% 5-HBB(F, F)-F 20.0% 3-H2BB(F, F)-F 10.0%5-HHBB(F, F)-F 3.0% 5-HHEBB-F 2.0% 3-HH2BB(F, F)-F 3.0% 1O1-HBBH-5 4.0%

Composition Example 37

3-D2B(F)-CF2OB(F)-CF3 5.0% (Compound No. 317) 3-D2HB(CL)-OCF2H 5.0%(Compound No. 40) 5-HB-F 12.0% 6-HB-F 9.0% 7-HB-F 7.0% 2-HHB-OCF3 7.0%3-HHB-OCF3 7.0% 4-HHB-OCF3 7.0% 5-HHB-OCF3 5.0% 3-HH2B-OCF3 4.0%5-HH2B-OCF3 4.0% 3-HHB(F, F)-OCF3 5.0% 3-HBB(F)-F 10.0% 3-HH2B(F)-F 3.0%3-HB(F)BH-3 3.0% 5-HBBH-3 3.0% 3-HHB(F, F)-OCF2H 4.0%

Composition Example 38

2-DH2B(F)-F 5.0% (Compound No. 51) 2-HD2B(F)-CF3 5.0% (Compound No. 46)2-D2BEB-CL 5.0% (Compound No. 311) 3-D2B(F)CF2OB(F)-CF3 5.0% (CompoundNo. 317) 3-D2HB(CL)-OCF2H 5.0% (Compound No. 40) 1-HD2B(F)B(F,F)-OCF2CFHCF3 3.0% (Compound No. 236) 3-D2B(F, F)B(F)B(F)-OCF2H 3.0%(Compound No. 228) 2-HHB(F)-F 2.0% 3-HHB(F)-F 2.0% 5-HHB(F)-F 2.0%3-HBB(F)-F 6.0% 5-HBB(F)-F 10.0% 3-H2BB(F)-F 9.0% 3-HBB(F, F)-F 20.0%5-HBB(F, F)-F 14.0% 1O1-HBBH-5 4.0%

Composition Example 39

3-D2B-CF3(Compound No. 11) 5.0% 3-D4B-CF3(Compound No. 261) 5.0%3-DHB(F)-OCF3 8.0% (Compound No. 22) 2-HHB(F)-F 11.0% 3-HHB(F)-F 11.0%5-HHB(F)-F 10.0% 2-H2HB(F)-F 10.0% 3-H2HB(F)-F 5.0% 5-H2HB(F)-F 10.0%2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F 13.0% T_(N1) = 77.3(° C.) η =27.8 (mPa.s) Δ n = 0.085 Δ ε 1 = 6.6 V_(th) = 1.86(V)

Composition Example 40

3-DHB(F)-OCF3 6.0% (Compound No. 22) 3-DHB(F, F)B(F)-Cl 10.0% (CompoundNo. 175) 7-HB(F, F)-F 3.0% 3-HB-O2 7.0% 2-HHB(F)-F 8.0% 3-HHB(F)-F 8.0%5-HHB(F)-F 8.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F 8.0% 2-HBB-F4.0% 3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB(F, F)-F 5.0% 5-HBB(F, F)-F 10.0%T_(N1) = 89.2(° C.) η = 35.8 (mPa.s) Δ n = 0.119 Δ ε 1 = 9.0 V_(th) =1.79(V)

Composition Example 41

3-D2B-CF3(Compound No. 11) 3.0% 3-D4B-CF3(Compound No. 261) 3.0%3-DHB(F, F)B(F)-Cl 9.0% (Compound No. 175) 3-HB-CL 6.0% 5-HB-CL 4.0%7-HB-CL 4.0% 1O1-HH-5 5.0% 2-HBB(F)-F 7.0% 3-HBB(F)-F 7.0% 5-HBB(F)-F7.0% 4-HHB-CL 8.0% 5-HHB-CL 8.0% 3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 8.0%5-H2BB(F, F)-F 9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0% T_(N1) = 90.3(°C.) η = 33.1 (mPa.s) Δ n = 0.127 Δ ε 1 = 6.9 V_(th) = 2.12(V)

Composition Example 42

3-D2B-CF3(Compound No. 11) 5.0% 3-D4B-CF3(Compound No. 261) 5.0%3-DHB(F)-OCF3 10.0% (Compound No. 22) 3-DHB(F, F)B(F)-Cl 10.0% (CompoundNo. 175) 3-HBB(F, F)-F 9.0% 3-H2HB(F, F)-F 6.0% 4-H2HB(F, F)-F 6.0%5-H2HB(F, F)-F 6.0% 3-HBB(F, F)-F 11.0% 5-HBB(F, F)-F 8.0% 3-H2BB(F,F)-F 8.0% 5-HHBB(F, F)-F 3.0% 5-HHEBB-F 2.0% 3-HH2BB(F, F)-F 3.0%1O1-HBBH-4 4.0% 1O1-HBBH-5 4.0% T_(N1) = 93.6(° C.) η = 44.1 (mPa.s) Δ n= 0.112 Δ ε 1 = 12.3 V_(th) = 1.57(V)

Composition Example 43

3-D2B-CF3(Compound No. 11) 5.0% 3-D4B-CF3(Compound No. 261) 5.0%3-DHB(F)-OCF3 12.0% (Compound No. 22) 5-HB-F 7.0% 6-HB-F 4.0% 7-HB-F7.0% 2-HHB-OCF3 7.0% 3-HHB-OCF3 7.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0%3-HHB(F, F)-OCF3 5.0% 3-HBB(F)-F 10.0% 5-HBB(F)-F 10.0% 3-HH2B(F)-F 3.0%3-HB(F)BH-3 3.0% 5-HBBH-3 3.0% 3-HHB(F, F)-OCF2H 4.0% T_(N1) = 65.0(°C.) η = 21.5 (mPa.s) Δ n = 0.089 Δ ε 1 = 7.2 V_(th) = 1.67(V)

Composition Example 44

3-DHB(F)-OCF3 10.0% (Compound No. 22) 3-DHB(F, F)B(F)-Cl 5.0% (CompoundNo. 175) 2-HHB(F)-F 2.0% 3-HHB(F)-F 2.0% 5-HHB(F)-F 2.0% 2-HBB(F)-F 6.0%3-HBB(F)-F 6.0% 5-HBB(F)-F 10.0% 2-H2BB(F)-F 9.0% 3-H2BB(F)-F 9.0%3-HBB(F, F)-F 15.0% 5-HBB(F, F)-F 19.0% 1O1-HBBH-4 5.0% T_(N1) = 91.1(°C.) η = 39.8 (mPa.s) Δ n = 0.130 Δ ε 1 = 9.4 V_(th) = 1.75(V)

Composition Example 45

3-DHB(F)-OCF3 15.0% (Compound No. 22) 3-H2HB(F, F)-F 7.0% 5-H2HB(F, F)-F8.0% 3-HHB(F, F)-F 10.0% 4-HHB(F, F)-F 5.0% 3-HH2B(F, F)-F 9.0%5-HH2B(F, F)-F 9.0% 3-HBB(F, F)-F 15.0% 3-HBEB(F, F)-F 2.0% 4-HBEB(F,F)-F 2.0% 5-HBEB(F, F)-F 2.0% 3-HHEB(F, F)-F 10.0% 4-HHEB(F, F)-F 3.0%5-HHEB(F, F)-F 3.0% T_(N1) = 81.0(° C.) η = 33.4 (mPa.s) Δ n = 0.086 Δ ε1 = 12.4 V_(th) = 1.69(V)

Composition Example 46

3-DHB(F)-OCF3 10.0% (Compound No. 22) 1V2-BEB(F, F)-C 5.0% 3-HB-C 15.0%1-BTB-3 5.0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 11.0% 3-HHB-3 9.0%3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 6.0%3-HB(F)TB-3 6.0% T_(N1) = 90.7(° C.) η = 23.1 (mPa.s) Δ n = 0.161 Δ ε 1= 9.4 V_(th) = 1.83(V)

Composition Example 47

3-D2B-CF3(Compound No. 11) 5.0% 3-D4B-CF3 (Compound No. 261) 5.0%3-DHB(F)-OCF3 4.0% (Compound No. 22) 3-O1-BEB(F)-C 12.0% 1V2-BEB(F, F)-C16.0% 3-HB-O2 5.0% 3-HH-4 3.0% 3-HHB-F 3.0% 3-HHB-1 8.0% 3-HHB-O1 4.0%3-HBEB-F 4.0% 3-HHEB-F 7.0% 5-HHEB-F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0%3-H2BTB-4 4.0% 3-HB(F)TB-2 5.0% T_(N1) = 80.6(° C.) η = 39.6 (mPa.s) Δ n= 0.131 Δ ε 1 = 26.8 V_(th) = 1.03(V)

Composition Example 48

3-D2B-CF3(Compound No. 11) 5.0% 3-DHB(F, F)B(F)-Cl 7.0% (Compound No.175) 2-HB-C 5.0% 3-HB-C 12.0% 3-HB-02 10.0% 2-BTB-1 3.0% 3-HHB-1 8.0%3-HHB-F 4.0% 3-HHB-O1 5.0% 3-HHB-3 14.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0%2-HHB(F)-F 7.0% 3-HHB(F)-F 7.0% 3-HHB(F, F)-F 5.0% T_(N1) = 96.8(° C.) η= 25.7 (mPa.s) Δ n = 0.097 Δ ε 1 = 7.0 V_(th) = 1.98(V)

Composition Example 49

3-DHB(F)-OCF3 4.0% (Compound No. 22) 3-DHB(F, F)B(F)-Cl 5.0% (CompoundNo. 175) 3-BEB(F)-C 8.0% 3-HB-C 4.0% V-HB-C 8.0% 1V-HB-C 8.0% 3-HB-O23.0% 3-HH-2V 14.0% 3-HH-2V1 7.0% V2-HHB-1 15.0% 3-HHB-1 5.0% 3-HHEB-F7.0% 3-H2BTB-2 6.0% 3-H2BTB-3 6.0% T_(N1) = 98.7(° C.) η = 22.0 (mPa.s)Δ n = 0.128 Δ ε 1 = 10.0 V_(th) = 2.06(V)

Description of the Preferred Embodiments

The following examples illustrate the present invention morespecifically. In each example, C represents a crystal, S×1 and S×2, eachindependently, represent a smectic phase different each other, Nrepresents a Nematic phase, and I represents a isotropic liquid phase.

EXAMPLE 1

Production of the compound (No. 21),5-propyl-2-(4-(3,4,5trifluorophenyl)-cyclohexyl)-1,3-dioxane (in formula(1), R=n-propyl group, n1=n2=0, A=(a), Za=Zb=a single bond, Q₁=Q₂=afluorine atom, Y=a fluorine atom)

1st Step

To Grignard reagent prepared from 3,4,5-trifluorobromobenzene 100 g (474mmol) and magnesium in 360 ml of dried tetrahydrofuran (abbreviated asTHF, hereinafter) at room temperature, a THF (500 ml) solution ofcyclohexanedione monoethyleneketal 74.0 g (474 mmol) was added dropwiseat room temperature, and the mixture was stirred for 5 hours at roomtemperature. The reactant was added to one liter of 6N-hydrochloricacid, and the product was extracted with diethylether. The extract waswashed with water, a saturated sodium bicarbonate aqueous solution, andthen water, and dried over anhydrous magnesium sulfate, and the solventwas distilled off under reduced pressure. To the residue, para-toluenesulfonic acid (abbreviated as PTS, hereinafter) 5 g and toluene 600 mlwere added. The mixture was refluxed with heating for 3 hours whileremoving water formed with Dien-Stark. The reactant was washed withwater, a saturated sodium bicarbonate aqueous solution, and then water,and dried over anhydrous magnesium sulfate, and the solvent wasdistilled off under reduced pressure. The residue was purified by silicagel column chromatography (eluent: heptane/ethyl acetate=4/1). Suchobtained purified material was hydrogenated in the presence of 5%palladium carbon 5 g as a catalyst in ethanol 300 ml. The catalyst wasfiltered off, the solvent was distilled off, and the residue waspurified by silica gel column chromatography (eluent: heptane/ethylacetate=3/1) to obtain 4-(3,4,5trifluorophenyl)cyclohexanone 52 g (228mmol). The yield was 48.1% from 3,4,5-trifluorobromobenzene.

2nd Step

To dried methoxymethyltriphenylphosphonium chloride (abbreviated as MTP,hereinafter) 25 g (72.9 mmol), THF 300 ml was added, andpotassium-t-butoxide 8.2 g (73.1 mmol) was added. The mixture wasstirred for about one hour. To the reactant, a THF solution (150 ml) ofthe above 4-(3,4,5-trifluorophenyl)cyclohexanone 14.8 g (64.9 mmol) wasadded dropwise, and the mixture was stirred for 2 hours. Water 300 mlwas added to the reactant, the product was extracted with toluene. Theextract was washed with a sodium chloride aqueous solution, dried overanhydrous magnesium sulfate, and the solvent was distilled off. Theresidue was purified by silica gel column chromatography (eluent:toluene). The resulting purified material was stirred in mixture solventof 3N-hydrochloric acid 200 ml and THF 200 ml for 5 hours, and theproduct was extracted with toluene. The extract was washed with asaturated sodium bicarbonate aqueous solution and then with water, anddried over anhydrous magnesium sulfate. Toluene was distilled off toobtain 4-(3,4,5-trifluorophenyl) cyclohexanecarboaldehyde 10.5 g (43.3mmol). The yield was 66.7% from 4-(3,4,5-trifluorophenyl) cyclohexanone.

3rd Step

2-propyl-1,3-propanediol 5.2 g (44.0 mol) and 4(3,4,5-trifluoro phenyl)cyclohexanecarboaldehyde 10.5 g (43.3 mmol) were dissolved in toluene100 ml, and PTS 1 g was added, and the mixture was refluxed with heatingfor 3 hours while removing water formed with Dien-Stark. The reactantwas washed with a saturated sodium bicarbonate aqueous solution, andthen with saturated sodium chloride aqueous solution, and dried overanhydrous magnesium sulfate, and the solvent was distilled off. Theresidue was recrystallized twice from heptane to obtain5-propyl-2-(4-(3,4,5-trifluorophenyl)cyclohexyl-1,3-dioxane 2.0 g (5.8mmol). The yield was 13% from 4-(3,4,5-trifluorophenyl)cyclohexanecarboaldehyde.

 ¹H-NMR(CDCl₃) δ(ppm): 6.88-6.71 (m,2H), 4.23-4.00(m,3H),3.42-3.17(m,2H), 2.48-0.82(m,18H)

 C-I point 92.8° C.

EXAMPLE 2

Production of the compound (No. 98),5-propyl-2-(2-(4-(3-fluoro-4-trifluoromethoxyphenyl)-3,5-difluorophenyl)ethyl)-1,3-dioxane(in general formula (1), R=n-propyl group, n1=0, n2=1, A=(b), Za=Zb=asingle bond, ring A1=3,5-difluoro-1,4-phenylene, Q₁=a fluorine atom,Q₂=a hydrogen atom, Y=a trifluoromethoxy group)

1st Step

Dimethoxyethane 350 ml was added to 60% sodium hydride 14.4 g (360mmol), the mixture was stirred at room temperature while a solution ofethyl diethylphosphonoacetate 80.7 g (360 mmol) in dimethoxyethane (50ml) was added dropwise. After the generation of hydrogen gas wasstopped, the solution was cooled to 15° C., and a solution of3,5-difluorobenzaldehyde 50.0 g (352 mmol) in dimethoxy ethane (50 ml)was added dropwise keeping the liquid temperature below 25° C. Afteraddition, the mixture was stirred for 30 minutes, the reactant was addedto water 300 ml, and the product was extracted with diethylether. Theextract was washed with a sodium chloride aqueous solution, and driedover anhydrous magnesium sulfate, and the solvent was distilled offunder reduced pressure. The residue was purified by silica gel columnchromatography (eluent: heptane/ethyl acetate=3/1). Such obtainedpurified material was hydrogenated in the presence of 5% palladiumcarbon as a catalyst in ethanol 300 ml. After hydrogenation, thecatalyst was filtered off, the solvent was distilled off under reducedpressure to obtain 3-(3,5-difluorophenyl) propionic acid ethyl ester53.0 g (247 mmol). The yield was 70.2% from 3,5-difluorobenzaldehyde.

2nd Step

The above 3-(3,5-difluorophenyl)propionic ethyl ester 53.0 g (247 mmol)was dissolved in toluene 500 ml and cooled to −58° C. under stirring,and a 1.01 M of toluene solution 255 ml (258 mmol) of DIBAL was addeddropwise, and the mixture was stirred at −55° C. for 15 minutes. At thesame temperature, a saturated ammonium chloride aqueous solution 200 mlwas added dropwise to the reactant, and the mixture was heated to roomtemperature and stirred for 30 minutes. Diethyl ether 100 ml was addedto the reactant, and the mixture was stirred at room temperature for onehour, and magnesium sulfate was added, and the suspension was filteredwith cerite. The filtrate was washed with water, the organic layer wasdried over magnesium sulfate, and the solvent was distilled off underreduced pressure to obtain 3(3,5-difluorophenyl)propanal 41.5 g. Theyield was 98.8% from 3-(3,5-difluorophenyl)propionic acid ethyl ester.

3rd Step

2-Propyl-1,3-propanediol 22.0 g (186 mol) and the above3-(3,5difluorophenyl)propanal 30.0 g (176 mmol) were dissolved intoluene 300 ml, and PTS 1 g was added, and the mixture was refluxed withheating for 3 hours while removing water formed with Dien-Stark. Thereactant was washed with a saturated sodium bicarbonate aqueoussolution, and then with saturated sodium chloride aqueous solution, anddried over anhydrous magnesium sulfate, and the solvent was distilledoff. The residue was recrystallized twice from heptane to obtain5-propyl-2-(4-(3,5-difluorophenyl)ethyl)-1,3-dioxane 7.50 g (27.7 mmol).The yield was 15.7% from 3-(3,5-difluorophenyl)propanal.

4th Step

The above 5-propyl-2-(4(3,5-difluorophenyl)ethyl)-1,3-dioxane 7.50 g(27.7 mmol) was dissolved in THF 70 ml, and cooled to −60° C. under anitrogen atmosphere. To this solution, 1.60 M hexane solution 21.0 ml(33.6 mmol) of n-butyllithium was added dropwise keeping the liquidtemperature below −50° C., and the mixture was stirred for one hour atthe same temperature. Then, to the reactant, 0.5 M THF solution 67.2 ml(33.6 mmol) of zinc chloride was added dropwise keeping the liquidtemperature below −50 ° C., and the mixture was heated to roomtemperature and stirred for 30 minutes. Tetrakistriphenyl phosphinparadium 0.5 g and 3-fluoro-4-trifluoromethoxybromobenzene 8.70 g (33.6mmol) were added to the solution, and the mixture was refluxed withheating for 3 hours. Water 100 ml was added to the resulting reactant,and the product was extracted with toluene. The extract was washed with3N-hydrochloric acid, a saturated bicarbonate aqueous solution and thena saturated sodium chloride aqueous solution, and dried over magnesiumsulfate, and the solvent was distilled off The residue was purified bysilica gel column chromatography (eluent: toluene), and recrystallizedtwice from a mixed solvent of heptane/ethyl acetate=1/1 to obtain5-propyl-2-(2-(4-(3-fluoro-4-trifluoromethoxyphenyl)-3,5-difluorophenyl)ethyl)-1,3-dioxane1.60 g (3.57 mmol). The yield was 12.9% from5-propyl-2-(4-(3,5-difluorophenyl)ethyl)-1,3-dioxane.

 ¹H-NMR(CDCl₃) δ(ppm): 7.45-7.24 (m,3H), 6.90-6.80(m,2H), 4.46(t,1H),4.19-4.01(m,2H), 3.44-3.19(m,2H), 2.85-2.16(m,2H), 1.28-0.82(m,9H)

 C-I point 57.8° C.

EXAMPLE 3

Production of the compound (No. 22), 5-propyl-2-(4-(3-fluoro-4-trifluoromethoxyphenyl)cyclohexyl)-1,3-dioxane (in formula (1), R=n-propyl group,n1=n2=0, A=(a), Za=Zb=a single bond, Q₁=a fluorine atom, Q₂=a hydrogenatom, Y=a trifluoromethoxy group)

1st Step

To Grignard reagent prepared from 3-fluoro-4-trifluoromethoxybromobenzene 70.0 g (270 mmol) and magnesium in dried THF 300 ml at roomtemperature, a THF (200 ml) solution of cyclohexanedionemonoethyleneketal 42.1 g (270 mmol) was added dropwise at roomtemperature, and the mixture was stirred for 3 hours at roomtemperature. The reactant was added to one liter of 6N-hydrochloricacid, and the product was extracted with diethylether. The extract waswashed with water, a saturated sodium bicarbonate aqueous solution, andthen water, and dried over anhydrous magnesium sulfate, and the solventwas distilled off under reduced pressure. To the residue, para-toluenesulfonic acid 5 g and toluene 500 ml were added. The mixture wasrefluxed with heating for 3 hours while removing water formed withDien-Stark. The reactant was washed with water, a saturated sodiumbicarbonate aqueous solution, and then water, and dried over anhydrousmagnesium sulfate, and the solvent was distilled off under reducedpressure. The residue was purified by silica gel column chromatography(eluent: heptane/ethyl acetate=4/1). Such obtained purified material washydrogenated in the presence of 5% palladium carbon 5 g as a catalyst inethanol 300 ml. The catalyst was filtered off, the solvent was distilledoff under reduced pressure, formic acid 20 g and toluene 200 ml wereadded to the residue, and the mixture was refluxed for 3 hours. Aftercooling, water 300 ml was added to the reactant, and the organic layerwas fractionated, washed with water, a saturated sodium bicarbonateaqueous solution, and then water, and dried over anhydrous magnesiumsulfate, and the solvent was distilled off. The residue was purified bysilica gel column chromatography (eluent: heptane/ethyl acetate=3/1) toobtain 4-(3-fluoro-4-trifluoromethoxyphenyl)cyclohexanone 22.0 g (84.5mmol). The yield was 31.3% from 3-fluoro-4-trifluoromethoxybromobenzene.

2nd Step

To dried MTP 10.0 g (29.2 mmol), THF 100 ml was added, andpotassium-t-butoxide 3.30 g (29.4 mmol) was added. The mixture wasstirred for about one hour. To the reactant, a Th solution (50 ml) ofthe above 4-(3-fluoro-4-trifluoromethoxyphenyl)cyclohexanone 6.0 g (23.1mmol) was added dropwise, and the mixture was stirred for 2 hours. Water150 ml was added to the reactant, the product was extracted withdiethylether. The extract was washed with a sodium chloride aqueoussolution, dried over anhydrous magnesium sulfate, and the solvent wasdistilled off. The residue was purified by silica gel columnchromatography (eluent: toluene). The resulting purified material wasstirred in mixture solvent of 3N-hydrochloric add 200 ml and acetone 200ml for 5 hours, and the product was extracted with toluene. The extractwas washed with a saturated sodium bicarbonate aqueous solution and thenwith water, and dried over anhydrous magnesium sulfate. Toluene wasdistilled off to obtain4(3-fluoro-4-trifluoromethoxyphenyl)cyclohexanecarboaldehyde 3.6 g (13.3mmol). The yield was 57.6% from 4-(3-fluoromethoxy phenyl)cyclohexanone.

3rd Step

2-Propyl-1,3-propanediol 2.2 g (18.5 mol) and4-(3-fluoro-4-trifluoromethoxyphenyl) cyclohexanecarboaldehyde 3.6 g(13.3 mmol) were dissolved in toluene 50 ml, and PTS 0.5 g was added,and the mixture was refluxed with heating for 3 hours while removingwater formed with Dien-Stark. The reactant was washed with a saturatedsodium bicarbonate aqueous solution, and then with saturated sodiumchloride aqueous solution, and dried over anhydrous magnesium sulfate,and the solvent was distilled off. The residue was recrystallized twicefrom heptane to obtain 5-propyl-2-(4-(3-fluoro-4-trifluoromethoxyphenyl)cyclohexyl-1,3-dioxane 1.22 g (3.12 mmol). The yield was 23.5%from 4-(3-fluoro-4-trifluoromethoxyphenyl)cyclohexanecarboaldehyde.

 ¹H-NMR(CDCl₃) δ(ppm): 7.18-6.82 (m,3H), 4.14-3.90(m,3H),3.23-3.07(m,2H), 2.38(m,1H), 1.92-0.72(m,16H)

 C-S×1 point 52.0° C., S×1-S×2 point 83.2° C., S×2-I point 117.5° C.

EXAMPLE 4

Production of the compound (No. 11), 5-propyl-2-(2-(4-trifluoromethylphenyl)ethyl-1,3-dioxane (in formula (1), R=n-propyl group,n1=n2=0, A=(b), Za=Zb =a single bond, Q₁=Q₂=a hydrogen atom, Y=atrifluoromethyl group)

1st Step

Dimethoxyethane 700 ml was added to 60% sodium hydride 24.8 g (620mmol), the mixture was stirred at room temperature while a solution ofethyl diethylphosphonoacetate 139 g (620 mmol) in dimethoxyethane (100ml) was added dropwise. After the generation of hydrogen gas wasstopped, the solution was cooled to 10° C., and a solution of4-trifluoromethylbenzaldehyde 100 g (574 mmol) in dimethoxyethane (100ml) was added dropwise keeping the liquid temperature below 25° C. Afteraddition, the mixture was stirred for 30 minutes, the reactant was addedto water one liter, and the product was extracted with diethylether. Theextract was washed with a sodium chloride aqueous solution, and driedover anhydrous magnesium sulfate, and the solvent was distilled offunder reduced pressure. The residue was purified by silica gel columnchromatography (eluent: heptane/ethyl acetate=3/1). Such obtainedpurified material was hydrogenated in the presence of 5% palladiumcarbon as a catalyst in ethanol 300 ml. The catalyst was filtered off,the solvent was distilled off at reduced pressure to obtain3-(4-trifluoromethylphenyl)propionic acid ethylester 81.0 g (329 mmol).The yield was 57.3% from 4-trifluoro methylbenzaldehyde.

2nd Step

The above 3-(4-trifluoromethylphenyl)propionic acid ethylester 81.0 g(329 mmol) was stirred in toluene 500 ml while the temperature wascooled to −60° C., and a 1.01 M of toluene solution 329 ml (332 mmol) ofDIBAL was added dropwise, and the mixture was stirred at −55° C. for 15minutes. At the same temperature, a saturated ammonium chloride aqueoussolution 200 ml was added dropwise to the reactant, and the mixture washeated to room temperature and stirred for 30 minutes. Ether 100 ml wasadded to the reactant, and the mixture was stirred at room temperaturefor one hour, and magnesium sulfate was added, and the suspension wasfiltered with cerite. The filtrate was washed with water, the organiclayer was dried over magnesium sulfate, and the solvent was distilledoff under reduced pressure. The residue was purified by silica gelcolumn chromatography (eluent: toluene) to obtain3-(4-trifluoromethylphenyl)propanal 62.5 g (309 mmol). The yield was93.9% from 3-(4-trifluorophenyl)propionic acid ethylester.

3rd Step

2-Propyl-1,3-propanediol 17.4 g (147 mol) and the above3-(4-trifluoromethylphenyl)propanal 20.0 g (98.9 mmol) were dissolved intoluene 200 ml, and PTS 1 g was added, and the mixture was refluxed withheating for 3 hours while removing water formed with Dien-Stark. Thereactant was washed with a saturated sodium bicarbonate aqueoussolution, and then with saturated sodium chloride aqueous solution, anddried over anhydrous magnesium sulfate, and the solvent was distilledoff. The residue was purified by silica gel column chromatography(eluent: toluene), and recrystallized twice from ethanol to obtain5-propyl-2-(2-(4-trifluoromethylphenyl)ethyl)-1,3-dioxane 10.8 g (35.7mmol). The yield was 36.1% from 3-(4-trifluoromethylphenyl) propanal.

 ¹H-NMR(CDCl₃) δ(ppm): 7.41 (dd,4H), 4.41(t,1H), 4.18-4.00(m,2H),3.41-3.16(m,2H), 2.88-2.70(m,2H), 2.14-1.80(m,3H), 1.35-0.81(m,7H)

 C-I point 72.6° C.

EXAMPLE 5

Production of the compound (No. 261), 5-propyl-4-(2-(4-trifluoromethylphenyl)butyl-1,3-dioxane (in formula (1), R=n-propyl group,n1=n2=0, A=(c), Za=Zb=a single bond, Q₁=Q₂=a hydrogen atom, Y=atrifluoromethyl group)

1st Step

Dimethoxyethane 180 ml was added to 60% sodium hydride 6.52 g (163mmol), the mixture was stirred at room temperature while a solution ofethyl diethylphosphonoacetate 36.5 g (163 mmol) in dimethoxyethane (50ml) was added dropwise. After the generation of hydrogen gas wasstopped, the solution was cooled to 5° C., and a solution of3-(4-trifluoromethylphenyl)propanal 30.0 g (148 mmol), which wasobtained in 3rd step of Example 4, in dimethoxyethane (50 ml) was addeddropwise keeping the liquid temperature below 25 ° C. After addition,the mixture was stirred for 30 minutes at room temperature, the reactantwas added to water 200 ml, and the product was extracted withdiethylether. The extract was washed with a sodium chloride aqueoussolution, and dried over anhydrous magnesium sulfate, and the solventwas distilled off under reduced pressure. The residue was purified bysilica gel column chromatography (eluent: heptane/ethyl acetate=3/1).Such obtained purified material was hydrogenated in the presence of 5%palladium carbon as a catalyst in ethanol 300 ml. After hydrogenation,the catalyst was :filtered off, the solvent was distilled off at reducedpressure to obtain 5-(4-trifluoro methylphenyl)pentanoic acid ethylester13.3 g (48.5 mmol). The yield was 32.8% from3-(4-trifluoromethylphenyl)propanal.

2nd Step

The above 5-(4-trifluoromethylphenyl)pentanoic acid ethylester 12.2 g(44.5 mmol) was stirred in toluene 70 ml while the temperature wascooled to −60° C., and a 1.01 M of toluene solution 46.0 ml (46.5 mmol)of DIBAL was added dropwise, and the mixture was stirred at −60° C. for15 minutes. At the same temperature, a saturated ammonium chlorideaqueous solution 40 ml was added dropwise to the reactant, and themixture was heated to room temperature and stirred for 30 minutes.Diethyl ether 100 ml was added to the reactant, and the mixture wasstirred at room temperature for one hour, and magnesium sulfate wasadded, and the suspension was filtered with cerite. The filtrate waswashed with water, the organic layer was dried over magnesium sulfate,and the solvent was distilled off under reduced pressure. The residuewas purified by silica gel column chromatography (eluent: toluene) toobtain 5-(4-trifluoromethylphenyl)pentanal 7.50 g (32.6 mmol). The yieldwas 73.3% from 5-(4-trifluorophenyl)pentanoic add ethylester.

3rd Step

2-Propyl-1,3-propanediol 5.90 g (49.9 mmol) and the above5-(4-trifluoromethylphenyl)pentanal 7.50 g (32.6 mmol) were dissolved intoluene 70 ml, and PTS 1 g was added, and the mixture was refluxed withheating for 3 hours while removing water formed with Dien-Stark. Thereactant was washed with a saturated sodium bicarbonate aqueoussolution, and then with saturated sodium chloride aqueous solution, anddried over anhydrous magnesium sulfate, and the solvent was distilledoff. The residue was purified by silica gel column chromatography(eluent: toluene), and recrystallized twice from ethanol to obtain5-propyl-2-(4-(4-trifluoromethylphenyl)butyl)-1,3-dioxane 5.55 g (16.7mmol). The yield was 51.2% from 5-(4-trifluoromethylphenyl) pentanal.

 ¹H-NMR(CDCl₃) δ(ppm): 7.40 (dd,4H), 4.42(t,1H), 4.16-3.98(m,2H;),3.41-3.16(m,2M), 2.76-2.59(m,2H), 2.10-0.81(m,14H)

 C-I point 50.9° C.

EXAMPLE 6

Production of the compound (No. 175),5-propyl-2-(4-(4-(3-fluoro-4-chlorophenyl)-3,5-difluorophenyl)cyclohexyl)-1,3-dioxane(in formula (1), R=n-propyl group, n1=0, n2=1, A=(a), ringA1=3,5-difluoro-1,4-phenylene, Za=Zb=a single bond, Q₁=a fluorine atom,Q₂=a hydrogen atom, Y=a chlorine atom)

1st Step

To Grignard reagent prepared from 3,5-difluorobromobenzene 100 g (518mmol) and magnesium in dried THF 300 ml at room temperature, a THF (300ml) solution of cyclohexanedione monoethyleneketal 74.6 g (517 mmol) wasadded dropwise at room temperature, and the mixture was stirred for 3hours at room temperature. The reactant was added to one liter of2N-hydrochloric acid, and the product was extracted with diethylether.The extract was washed with water, a saturated sodium bicarbonateaqueous solution, and then water, and dried over anhydrous magnesiumsulfate, and the solvent was distilled off under reduced pressure. Tothe residue, para-toluene sulfonic acid 5 g and toluene 800 ml wereadded. The mixture was refluxed with heating while removing water formedwith Dien-Stark. The reactant was washed with water, a saturated sodiumbicarbonate aqueous solution, and then water, and dried over anhydrousmagnesium sulfate, and the solvent was distilled off under reducedpressure. The residue was purified by silica gel column chromatography(eluent: heptane/ethyl acetate=3/1). Such obtained purified material washydrogenated in the presence of 5% palladium carbon 5 g as a catalyst inethanol 500 ml. The catalyst was filtered off, the solvent was distilledoff under reduced pressure, formic acid 40 g and toluene 300 ml wereadded to the residue, and the mixture was refluxed for 3 hours. Aftercooling, water 500 ml was added to the reactant, and the organic layerwas fractionated, washed with water, a saturated sodium bicarbonateaqueous solution, and then water, and dried over anhydrous magnesiumsulfate, and the solvent was distilled off. The residue was purified bysilica gel column chromatography (eluent: heptane/ethyl acetate=3/1) toobtain 4-(3,5-difluorophenyl)cyclohexanone 29.4 g (140 mmol). The yieldwas 27.0% from 3,5-difluorobromobenzene.

2nd Step

To dried MTP 10.0 g (29.2 mmol), THF 100 ml was added, andpotassium-t-butoxide 3.30 g (29.4 mmol) was added. The mixture wasstirred for about one hour. To the reactant, a THF solution (50 ml) ofthe above 4-(3,5-difluorophenyl)cyclohexanone 5.0 g (23.8 mmol) wasadded dropwise, and the mixture was stirred for 2 hours. Water 150 mlwas added to the reactant, the product was extracted with diethylether.The extract was washed with a sodium chloride aqueous solution, driedover anhydrous magnesium sulfate, and the solvent was distilled off. Theresidue was purified by silica gel column chromatography (eluent:toluene). The resulting purified material was stirred in mixture solventof 3N-hydrochloric add 200 ml and acetone 200 ml for 5 hours at roomtemperature, and the product was extracted with toluene. The extract waswashed with a saturated sodium bicarbonate aqueous solution and thenwith water, and dried over anhydrous magnesium sulfate. Toluene wasdistilled off to obtain 4-(3,5-difluorophenyl)cyclohexanecarboaldehyde5.0 g (22.3 mmol). The yield was 93.7% from 4-(3,5-difluorophenyl)cyclohexanone.

3rd Step

2-Propyl-1,3-propanediol 3.5 g (29.6 mol) and 4-(3,5-difluorophenyl)cyclohexanecarboaldehyde 5.0 g (22.3 mmol) were dissolved in toluene 50ml, and PTS 0.5 g was added, and the mixture was refluxed with heatingfor 3 hours while removing water formed with Dien-Stark. The reactantwas washed with a saturated sodium bicarbonate aqueous solution, andthen with saturated sodium chloride aqueous solution, and dried overanhydrous magnesium sulfate, and the solvent was distilled off. Theresidue was recrystallized twice from heptane to obtain5-propyl-2-(4-(3,5-difluorophenyl)cyclohexyl-1,3-dioxane 2.3 g (7.1mmol). The yield was 24.0% from 4-(3,5-difluorophenyl)cyclohexanecarboaldehyde.

4th Step

The above 5-propyl-2-(4-(3,5-difluorophenyl)cyclohexyl-1,3-dioxane 1.3 g(4.0 mmol) was dissolved in THF 10 ml, and cooled to −65° C. under anitrogen atmosphere. To this solution, 1.68 M hexane solution 3.0 ml(5.0 mmol) of n-butyllithium was added dropwise keeping the liquidtemperature below −55° C., and the mixture was stirred for one hour atthe same temperature. Then, to the reactant, 0.5 M THF solution 10 ml(5.0 mmol) of zinc chloride was added dropwise keeping the liquidtemperature below −50° C., and the mixture was heated to roomtemperature and stirred for 30 minutes. Tetrakistriphenylphosphinparadium 0.5 g and 3-fluoro-4-chlorobromobenzene 1.1 g (5.3 mmol) wereadded to the solution, and the mixture was refluxed with heating for 3hours. Water 30 ml was added to the resulting reactant, and the productwas extracted with toluene. The extract was washed with 3N-hydrochloricacid, a saturated bicarbonate aqueous solution and then a saturatedsodium chloride aqueous solution, and dried over magnesium sulfate, andthe solvent was distilled off. The residue was purified by silica gelcolumn chromatography (eluent: toluene), and recrystallized twice from amixed solvent of heptane/ethyl acetate=1/1 to obtain5-propyl-2-(4-(4-(3-fluoro-4-chlorophenyl)-3,5-difluorophenyl)cyclohexyl)-1,3-dioxane 1.7 g (3.8 mmol). The yield was 95.0% from5-propyl-2-(4-(3,5-difluorophenyl)ethyl)-1,3-dioxane.

 ¹H-NMR(CDCl₃) δ(ppm): 7.54-7.14 (m,3H), 6.95-6.72(m,2H),4.25-4.01(m,3H), 3,43-3.18(m,2H), 2.63-2.37(m, 1H), 2.04-0.82(m, 17H)

 C-N point 110.1° C., N-I point 227.9° C.

EXAMPLE 7

Production of the compound (No. 362), 4-(5-pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid 3,4,5-trifluorophenylester (in formula (1),R=n-pentyl group, n1=n2=0, A=(a), Za=a single bond, Zb=—COO—, Q₁=Q₂=afluorine atom, Y=a fluorine atom)

1st Step

To dried MTP 50.0 g (146 mmol), THF 500 ml was added, andpotassium-t-butoxide 18.0 g (160 mmol) was added. The mixture wasstirred for about one hour. To the reactant, a THF solution (100 ml) of4-oxocyclohexane carboxylic acid methylester 21.9 g (140 mmol) was addeddropwise, and the mixture was stirred for 2 hours. Water 500 ml wasadded to the reactant, the product was extracted with diethylether. Theextract was washed with a sodium chloride aqueous solution, dried overanhydrous magnesium sulfate, and the solvent was distilled off. Theresidue was purified by silica gel column chromatography (eluent:toluene). Such resulting purified material was stirred in mixed solventof 2N-hydrochloric acid 500 ml and acetone 500 ml for 5 hours at roomtemperature, and the product was extracted with toluene. The extract waswashed with a saturated sodium bicarbonate aqueous solution and thenwith water, and dried over anhydrous magnesium sulfate. Toluene wasdistilled off to obtain 4-formylcyclohexane carboxylic acid methyl ester18.8 g (111 mmol). The yield was 79.2% from 4-oxocyclohexane carboxylicacid methylester.

2nd Step

2-Pentyl-1,3-propanediol 17.0 g (116 mol) and 4-formylcyclohexanecarboxylic acid methyl ester 18.8 g (111 mmol) were dissolved in toluene120 ml, and PTS 1.0 g was added, and the mixture was refluxed withheating for 3 hours while removing water formed with Dien-Stark. Thereactant was washed with a saturated sodium bicarbonate aqueoussolution, and then with saturated sodium chloride aqueous solution, anddried over anhydrous magnesium sulfate, and the solvent was distilledoff. The residue was purified by silica gel column chromatography(eluent: toluene/ethyl acetate=4/1) to obtain4-(5-pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid methylester 28.2g (94.5 mmol). The yield was 85.1% from 4-formylcyclohexanecarboxylicacid methylester.

3rd Step

4-(5-Pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid methylester 28.2g (94.5 mmol) was added in ethanol 100 ml, and cooled to 7° C., and2N-sodium hydroxide 70 ml was added dropwise. The mixture was heated toroom temperature, and stirred for one hour, and 2N-sodium hydroxide 70ml was added dropwise. After st g the mixture father one hour at roomtemperature, 2N-sodium hydroxide 50 ml was added dropwise, and themixture was stirred further one hour at room temperature.6N-Hydrochloric acid 65 ml was added to the reactant, and the productwas extracted with diethylether. The extract was washed with water, asaturated sodium bicarbonate aqueous solution and then water, and driedover magnesium sulfate, and the solvent was distilled off. The residue27.3 g was purified by silica gel column chromatography (eluent:toluene/ethyl acetate=1/1), and recrystallized from a mixed solvent ofheptane/ethanol =20/1 to obtain4-(5-pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid 2.3 g (8.1mmol). The yield was 8.6% from 4-(5-pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid methylester.

4th Step

To 200 ml of three necked flask equipped with a calcium chloride tube,methylene chloride 10 ml, the said⁴-(5-pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid 1.5 g (5.3mmol), 3,4,5-trifluorophenol 1.0 g (6.9 mmol) and4-dimethylaminopyridine 0.2 g (1.6 mmol) were charged, and the mixturewas cooled to 0° C. with stirring, and a solution ofdicyclohexylcarbodiimide 1.6 g (7.9 mmol) in methylene chloride (8 ml)was added dropwise for two minutes. The mixture was heated to roomtemperature and stirred at the same temperature for 3 hours. Thereactant was filtered, and the filtrate was washed with 5N-hydrochloricacid 20 ml, and again filtered. The filtrate was washed with a saturatedsodium bicarbonate aqueous solution and then water, and dried overmagnesium sulfate, and the solvent was distilled off under reducedpressure. The residue was purified by silica gel column chromatography(eluent: toluene/ethyl acetate=4/1), and recrystallized from ethanol andthen fom a mixed solvent of ethanol/heptane=9/1 to obtain4-(5-pentyl-(1,3-dioxane)-2-yl)cyclo hexanecarboxylic acid3,4,5-trifluorophenylester 1.30 g (3.1 mmol). The yield was 58% from4-(5-pentyl-(1,3-dioxane)-2-yl)cyclohexanecarboxylic acid.

 ¹H-NMR(CDCl₃) δ(ppm): 6.89-6.69(m,2H), 4.22-3.99(m,3H),3.41-3.15(m,2H), 2.61-0.81(m,22H)

 C-N point 62.1° C., N-I point 74.6° C., (N-SA point 49.3° C.)

EXAMPLE 8

Production of the compound (No. 352),1-(2-(1,3-dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene (informula (1), R=a hydrogen atom, n1=0, n2=1, A=(b), ringA1=1,4-cyclohexylene, Za=Zb=a single bond, Q₁=Q₂=a fluorine atom, Y=afluorine atom)

1st Step

To dried 1,3-dioxane-2-ylethyltriphenylphosphoniumbromide 48.0 g (105mmol), THF 500 ml was added, and potassium-t-butoxide 11.8 g (105 mmol)was added. The mixture was stirred for about one hour. To the reactant,a THF solution (200 ml) of 4-(3,5-difluorophenyl)cyclohexanone 20.0 g(87.6 mmol), which was obtained by the said 1st step of Example 6, wasadded dropwise at room temperature, and the mixture was stirred for 2.5hours. Water 500 ml was added to the reactant, the product was extractedwith toluene. The extract was washed with a sodium chloride aqueoussolution, dried over anhydrous magnesium sulfate, and the solvent wasdistilled off. The residue was purified by silica gel columnchromatography (eluent: toluene). Such obtained purified material washydrogenated in the presence of 5% palladium carbon as a catalyst inethanol 100 ml. The catalyst was filtered off, the filtrate wasconcentrated, the resulting residue was purified by silica gel columnchromatography (eluent: toluene) and recrystallized from ethanol toobtain 1-(2-(1,3-dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene15.2 g (46.3 mmol). The yield was 52.9% from4-(3,5-difluorophenyl)cyclohexanone.

 C-I point 69.8° C.

EXAMPLE 9

Production of the compound (No. 33),1-(2-(5-propyl-1,3-dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene(in formula (1), R=n-propyl group, n1=0, n2=1, A=(b), ringA1=1,4-cyclohexylene, Za=Zb=a single bond, Q₁=Q₂=a fluorine atom, Y=afluorine atom)

1st Step

1-(2-(1,3-Dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene 3.7 g (11mmol) obtained in Example 8 and formic acid 25.0 g (540 mmol) were addedto toluene 20 ml, and the mixture was refluxed with heating for 3 hours.The reactant was cooled to room temperature, water 100 ml was added, andthe product was extracted with toluene. The extract was washed withwater, a saturated sodium bicarbonate aqueous solution, and water, anddried over anhydrous magnesium sulfate, and the solvent was distilledoff to obtain crude 3-(4-(3,4,5-trifluorophenyl)cyclohexyl)propanal 3.5g. The product and 2-propyl-1,3-propanediol 2.3 g (20 mmol) weredissolved in toluene 20 ml, PTS 0.5 g was added. The mixture wasrefluxed with heating for 3 hours while removing water formed withDien-Stark. The reactant was washed with a saturated sodium bicarbonateaqueous solution, and then with saturated sodium chloride aqueoussolution, and dried over anhydrous magnesium sulfate, and the solventwas distilled off. The residue was purified by silica gel columnchromatography (eluent: toluene) and recrystallized twice from ethanolto obtain1-(2-(5-propyl-1,3-dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene1.4 g (3.8 mmol). The yield was 34.5% from1-(2-(1,3-dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene.

 ¹H-NMR(CDCl₃) δ(ppm): 6.87-6.70(m,2H), 4.42(t,1H), 4.17-3.99(m,2H),3.43-3.18(m,2H), 2.54-2.25(m,1H), 1.93-0.81(m,21H)

 C-I point 88.6° C.

Based on the description of Examples 1-9 and the column of the detaileddescription of the present specification, we can produce the followingcompounds of Nos. 1-370. In addition, the compounds of Examples 1-9 areadded again in the list.

EXAMPLE 10 (Using Example 1)

4-(4-propylcyclohexyl)benzonitrile 24%4-(4-pentylcyclohexyl)benzonitrile 36%4-(4-heptylcyclohexyl)benzonitrile 25%4-(4-(4-pentylcyclohexyl)phenylbenzonitrile 15%

A liquid crystal composition (A1) was prepared from the said fourcompounds. % is represented by weight, hereinafter. The clearing pointof the nematic liquid crystal composition is 71.7° C., the thresholdvoltage is 1.79 V at a cell thickness of 9.2 μm, Δε1 is 11.0, Δn is0.137, and the viscosity is 26.6 mPa.s at 20° C.

A liquid crystal composition (B1) is prepared from 85% of the aboveliquid crystal composition and 15% of5-propyl-2-(4-(3,4,5-trifluorophenyl)-cyclohexyl)-l,3-dioxane (CompoundNo. 21) obtained from Example 1. The clearing point of the compositionis 65.3° C., the threshold voltage is 1.46 V at a cell thickness of 9.2μm, Δε1 is 12.9, Δn is 0.126, and the viscosity is 32.3 mPa.s at 20° C.The properties of the compound No. 21 are calculated by extrapolationfrom the mixing ratio of the above compositions: clearing point is 29.0°C., Δε1 is 23.7, Δn is 0.064, and the viscosity is 64.6 mPa.s at 20° C.

EXAMPLE 11 (Comparing Example 1)

A liquid crystal composition (B1-R) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-(4-propylcyclohexyl)-2-(3,4,5-trifluorophenyl)-1,3-dioxane (Compoundof formula (14)). The clearing point of the composition is 69.6° C., thethreshold voltage is 1.60 V at a cell thickness of 9.2 μm, Δε1 is 11.7,Δn is 0.127, and the viscosity is 29.2 mPa.s at 20° C. The properties ofthe compound of formula (14) are calculated by extrapolation from themixing ratio of the above compositions: clearing point is 57.7° C., Δε1is 15.7, Δn is 0.070, and the viscosity is 43.9 mPa.s at 20° C.

From the result, comparing with the dioxane ring and the cyclohexanering of the compound of formula (14), those of the compound (No. 21) ofthe present invention are reversed. Accordingly, in comparison with thecompound of formula (14), the compound No. 21 of the present inventionshows, in spite of lower clearing point of 29° C., the Δε is increasedto about 1.5 times.

EXAMPLE 12 (Using Example 2)

A liquid crystal composition (B2) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-propyl-2-(2-(4-(3-fluoro-4-trifluoromethoxyphenyl)-3,5-difluorophenyl)ethyl)-1,3-dioxane(Compound No. 98) obtained from example 2. The clearing point of thecomposition is 652.8° C., the threshold voltage is 1.40 V at a cellthickness of 9.3 μm, Δε1 is 13.6, Δn is 0.132, and the viscosity is 33.8mPa.s at 20° C. The properties of the compound No. 98 are calculated byextrapolation from the mixing ratio of the above compositions: clearingpoint is 12.0° C., Δε is 28.3, Δn is 0.104, and the viscosity is 74.6mPa.s at 20° C.

EXAMPLE 13 (Comparing Example 2)

A liquid crystal composition (B2-R) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-propyl-2-(4-(3-fluoro-4trifluoromethoxyphenyl)-3,5-difluorophenyl)-1,3-dioxane(Compound of formula (17)). The clearing point of the composition is65.1° C., the threshold voltage is 1.40 V at a cell thickness of 9.1 μm,Δε1 is 13.2, Δn is 0.133, and the viscosity is 30.8 mPa.s at 20° C. Theproperties of the compound of formula (17) are calculated byextrapolation from the mixing ratio of the above compositions: clearingpoint is 27.7° C., Δε is 25.7, Δn is 0.110, and the viscosity is 54.6mPa.s at 20° C.

From the result, comparing with the compound of formula (17), thecompound No. 98 of the present invention has an ethylene group at2-position on the dioxane ring of the compound of formula (17), and theΔε is increased in about 3.3.

EXAMPLE 14 (Using Example 3)

A liquid crystal composition (B3) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-propyl-2-(4-(3-fluoro-4-trifluoromethoxyphenyl)-cyclohexyl-1,3-dioxane (Compound No. 22) obtained from Example3. The clearing point of the composition is 69.2° C., the thresholdvoltage is 1.56 V at a cell thickness of 9.3 μm, Δε1 is 12.2, Δn is0.128, and the viscosity is 30.0 mPa.s at 20° C. The properties of thecompound No. 22 are calculated by extrapolation from the mixing ratio ofthe above compositions: clearing point is 55.0° C., Δε1 is 19.0, Δn is0.077, and the viscosity is 49.3 mPa.s at 20° C.

EXAMPLE 15 (Using Example 4)

A liquid crystal composition (B4) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-propyl-2-(2-(4-trifluoromethylphenyl)ethyl-1,3-dioxane (Compound No.11) obtained from example 4. The clearing point of the composition is45.8° C., the threshold voltage is 1.39 V at a cell thickness of 9.1 μm,Δε1 is 11.4, Δn is 0.115, and the viscosity is 26.9 mPa.s at 20° C. Theproperties of the compound No. 11 are calculated by extrapolation fromthe mixing ratio of the above compositions: clearing point is −101.0°C., Δε1 is 13.7, and the viscosity is 28.5 mPa.s at 20° C.

EXAMPLE 16 (Using Example 5)

A liquid crystal composition (B5) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-propyl-4(2-(4-trifluoromethylphenyl)butyl-1,3-dioxane (Compound No.261) obtained from Example 5. The clearing point of the composition is45.2° C., the threshold voltage is 1.43 V at a cell thickness of 9.0 μm,Δε1 is 11.2, Δn is 0.116, and the viscosity is 27.9 mPa.s at 20° C. Theproperties of the compound No. 261 are calculated by extrapolation fromthe mixing ratio of the above compositions: clearing point is −105.0°C., Δε1 is 12.3, and the viscosity is 35.3 mPa.s at 20° C.

EXAMPLE 17 (Using Example 6)

A liquid crystal composition (B6) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of5-propyl-2-(4-(4-(3-fluoro-4-chlorophenyl)-3,5-difluorophenyl)cyclohexyl)-1,3-dioxane(Compound No. 175) obtained from example 6. The clearing point of thecomposition is 83.0° C., the threshold voltage is 1.70 V at a cellthickness of 8.9 μm, Δε1 is 14.0, Δn is 0.142, and the viscosity is 40.5mPa.s at 20° C. The properties of the compound No. 275 are calculated byextrapolation from the mixing ratio of the above compositions: clearingpoint is 147.0° C., Δε is 31.0 Δn is 0.170, and the viscosity is 119.1mPa.s at 20° C.

EXAMPLE 18 (Using Example 7)

A liquid crystal composition (B7) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of 4-(5-pentyl-1,3-dioxane-2-yl)cyclohexanecarboxylic acid 3,4,5-trifluorophenylester (Compound No. 362)obtained from Example 7. The clearing point of the composition is 70.3°C., the threshold voltage is 1.49 V at a cell thickness of 8.9 μm, Δε1is 12.2, Δn is 0.126, and the viscosity is 32.3 mPa.s at 20° C. Theproperties of the compound No. 362 are calculated by extrapolation fromthe mixing ratio of the above compositions: clearing point is 62.4° C.,Δε is 19.0, Δn is 0.064, and the viscosity is 64.9 mPa.s at 20° C.

EXAMPLE 19 (Using Example 8)

A liquid crystal composition (B8) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of 1-(2-(1,3-dioxane-2-yl)ethyl)cyclohexyl-3,4,5-trifluorobenzene (Compound No. 352) obtained fromExample 8. The clearing point of the composition is 50.0° C., thethreshold voltage is 1.40 V at a cell thickness of 8.9 μm, Δε1 is 12.8,Δn is 0.114, and the viscosity is 37.6 mPa.s at 20° C. The properties ofthe compound No. 352 are calculated by extrapolation from the mixingratio of the above compositions: clearing point is −73.0° C., Δε is23.0, and the viscosity is 100.2 mPa.s at 20° C.

EXAMPLE 20 (Using Example 9)

A liquid crystal composition (B9) is prepared from 85% of the aboveliquid crystal composition (A1) and 15% of1-(2-(5-propyl-1,3-dioxane-2-yl)ethyl) cyclohexyl-3,4,5-trifluorobenzene(Compound No. 33) obtained from Example 9. The clearing point of thecomposition is 65.7° C., the threshold voltage is 1.57 V at a cellthickness of 9.0 μm, Δε1 is 12.2, Δn is 0.124, and the viscosity is 34.2mPa.s at 20° C. The properties of the compound No. 33 are calculated byextrapolation from the mixing ratio of the above compositions: clearingpoint is 31.7° C., Δε is 19.0, Δn is 0.050, and the viscosity is 77.0mPa.s at 20° C.

Industrial Applicability

The compounds of the present invention are characterized by a highvoltage holding ratio and large Δε, by using the compounds of thepresent invention as constitutional components of liquid crystalcompositions, driving at low voltage can be realized with liquid crystaldisplay device of a TFT mode, which has been impossible hitherto.

What is claimed is:
 1. A dioxane derivative represented by generalformula (I):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom, n1 and n2, each independently, are an integer of 0-2, n1+n2≦2, Q₁and Q₂, each independently, are a hydrogen atom, fluorine atom orchlorine atom, A represents (a), (b) or (c),

ring A0 and A1 represent a 1,4-cyclohexylene group or a 1,4-phenylenegroup, in which 1 or more hydrogen atoms may be replaced by a fluorineatom or a chlorine atom, and one or two carbon atoms may be replaced bya silicon atom in the 1,4-cyclohexylene in A, ring A0 and ring A1, Zaand Zb, each independently, represent a single bond, —CH₂CH₂—,—CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—, Y represents a hydrogenatom, a halogen atom, or a halogenated alkyl group of 1-5 carbon atoms,in which one or more not-adjacent methylene groups may be replaced by anoxygen atom or a sulfur group, in the case of n1=0 and n2=1, and A is(b), ring A1 is

in the case of Y is a fluorine atom or a chlorine atom, Q1 and Q2, eachindependently, represent a fluorine atom or a chlorine atom; and in thecase of A is (a) and Zb is a single bond, n1+n2=1, further, each elementconstituting the compound may be replaced by its isotope.
 2. A dioxanederivative according to claim 1, wherein n1+n2=1, and A=(b).
 3. A liquidcrystal composition comprising at least one dioxane derivative accordingto claim 1 as the first component, and at least one compound selectedfrom the group consisting of compounds represented by general formulas(2), (3) and (4) as the second component,

wherein R₃ is an alkyl group of 1-10 carbon atoms, in the alkyl group,at least one not-adjacent methylene group may be replaced by an oxygenatom or —CH═CH—, and any hydrogen atom may be replaced by a fluorineatom, Y₁ represents a fluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃,CF₂H, CFH₂, OCF₂CF₂H or OCF₂CFHCF₃, L₁ and L₂, each independently,represent a hydrogen atom or a fluorine atom, Z₁ and Z₂, eachindependently, —CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —COO—, —CF₂O—, —OCF₂—, —CH═CH—or a single bond, ring B represents trans-1,4-cyclohexylene,1,3-dioxane-2,5-diyl or 1,4-phenylene, wherein the hydrogen atom may bereplaced by a fluorine atom, ring C represents trans-1,4-cyclohexyleneor 1,4-phenylene, wherein the hydrogen atom may be replaced by afluorine atom, and each element constituting the compound in eachformula may be replaced by its isotope.
 4. A liquid crystal compositioncomprising at least one dioxane derivative according to claim 1 as thefirst component, and at least one compound selected from the groupconsisting of compounds represented by general formulas (5) and (6) asthe second component,

wherein R₄ and R₅, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, Y₂ represents —CN or —C≡C—CN,ring E represents trans-1,4-cyclohexylene, 1,4-phenylene,1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl, ring G representstrans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene, whereinthe hydrogen atom may be replaced by a fluorine atom, ring H representstrans-1,4-cyclohexylene or 1,4-phenylene, Z₃ represents —CH₂CH₂—, —COO—or a single bond, L₃, L₄ and L₅, each independently, represent ahydrogen atom or a fluorine atom, b, c and d, each independently, are 0or 1, and each element constituting the compound in each formula may bereplaced by its isotope.
 5. A liquid crystal composition comprising atleast one dioxane derivative according to claim 1 as the firstcomponent, and at least one compound selected from the group consistingof compounds represented by the said general formulas (2), (3) and (4)as the second component, and at least one compound selected from thegroup consisting of compounds represented by general formulas (7), (8)and (9) as the third component,

wherein R₃ is an alkyl group of 1-10 carbon atoms, in the alkyl group,at least one not-adjacent methylene group may be replaced by an oxygenatom or —CH═CH—, and any hydrogen atom may be replaced by a fluorineatom, Y₁ represents a fluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃,CF₂H, CFH₂, OCF₂CF₂H or OCF₂CFHCF₃, L₁ and L₂, each independently,represent a hydrogen atom or a fluorine atom, Z₁ and Z₂, eachindependently, represent —CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —COO—, —CF₂O—,—OCF₂—, —CH═—CH— or a single bond, ring B representstrans-1,4-cyclohexylene, 1,3-dioxane2,5diyl or 1,4-phenylene, whereinthe hydrogen atom may be replaced by a fluorine atom, ring C representstrans-1,4-cyclohexylene or 1,4phenylene, wherein the hydrogen atom maybe replaced by a fluorine atom, and each element constituting thecompound in each formula may be replaced by its isotope,

wherein R₆ and R₇, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, I, J and K, each independently,represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4phenylene,wherein the hydrogen atom may be replaced by a fluorine atom, Z₄ and Z₅,each independently, represent —CH≡C—, —COO—, —CH₂CH₂—, —CH═CH— or asingle bond, and each element constituting the compound in each formulamay be replaced by its isotope.
 6. A liquid crystal compositioncomprising at least one dioxane derivative according to claim 1 as thefirst component, and at least one compound selected from the groupconsisting of compounds represented by the said general formulas (5) and(6) as the second component, and at least one compound selected from thegroup consisting of compounds represented by the said general formulas(7), (8) and (9) as the third component,

wherein R₄ and R₅, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom maybe replaced by a fluorine atom, Y₂ represents —CN or —C≡C—CN,ring E represents trans-1,4cyclohexylene, 1,4-phenylene,1,3-dioxane2,5-diyl or pyrimidine-2,5diyl, ring G representstrans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene, whereinthe hydrogen atom may be replaced by a fluorine atom, ring H representstrans-1,4cyclohexylene or 1,4-phenylene, Z₃ represents —CH₂CH₂—, —COO—or a single bond, L₃, L₄ and L₅, each independently, represent ahydrogen atom or a fluorine atom, b, c and d, each independently, are 0or 1, and each element constituting the compound in each formula may bereplaced by its isotope,

wherein R₆ and R₇, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, I, J and K, each independently,represent trans-1,4-cyclohexylene, pyrimidine-2,5diyl or 1,4-phenylene,wherein the hydrogen atom may be replaced by a fluorine atom, Z₄ and Z₅,each independently, represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH— or asingle bond, and each element constituting the compound in each formulamay be replaced by its isotope.
 7. A liquid crystal compositioncomprising at least one dioxane derivative according to claim 1 as thefirst component, and at least one compound selected from the groupconsisting of compounds represented by the said general formulas (2),(3) and (4) as a part of the second component, and at least one compoundselected from the group consisting of compounds represented by the saidgeneral formulas (5) and (6) as another part of the second component,and at least one compound selected from the group consisting ofcompounds represented by the said general formulas (7), (8) and (9) asthe third component,

wherein R₃ is an alkyl group of 1-10 carbon atoms, in the alkyl group,at least one not-adjacent methylene group may be replaced by an oxygenatom or —CH═CH—, and any hydrogen atom may be replaced by a fluorineatom, Y₁ represents a fluorine atom, a chlorine atom, OCF₃, OCF₂H, CF₃,CF₂H, CFH₂, OCF₂CF₂H or OCF₂CFHCF₃, L₁ and L₂ each independently,represent a hydrogen atom or a fluorine atom, Z₁ and Z₂, eachindependently, represent —CH₂CH₂—, —CH₂CH₂CH₂CH₂—, —COO—, —CF₂O—,—OCF₂—, —CH═CH— or a single bond, ring B representstrans-1,4-cyclohexylene, 1,3-dioxane-2,5diyl or 1,4-phenylene, whereinthe hydrogen atom may be replaced by a fluorine atom, ring C representstrans-1,4-cyclohexylene or 1,4-phenylene, wherein the hydrogen atom maybe replaced by a fluorine atom, and each element constituting thecompound in each formula may be replaced by its isotope,

wherein R₄ and R₅, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, Y₂ represents —CN or —C≡C—CN,ring E represents trans-1,4-cyclohexylene, 1,4-phenylene,1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl, ring G representstrans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene, whereinthe hydrogen atom may be replaced by a fluorine atom, ring H representstrans-1,4-cyclohexylene or 1,4-phenylene, Z₃ represents —CH₂CH₂—, —COO—or a single bond, L₃, L₄ and L₅, each independently, represent ahydrogen atom or a fluorine atom, b, c and d, each independently, are 0or 1, and each element constituting the compound in each formula may bereplaced by its isotope,

wherein R₆ and R₇, each independently, represent an alkyl group of 1-10carbon atoms, in the alkyl group, one or more not-adjacent methylenegroups may be replaced by an oxygen atom or —CH═CH—, and any hydrogenatom may be replaced by a fluorine atom, I, J and K, each independently,represent trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene,wherein the hydrogen atom maybe replaced by a fluorine atom, Z₄ and Z₅,each independently, represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH— or asingle bond, and each element constituting the compound in each formulamay be replaced by its isotope.
 8. A liquid crystal compositionaccording to claim 9 wherein the liquid crystal composition furthercontains an optically active compound.
 9. A liquid crystal devicecomprising a liquid crystal composition according to claim
 4. 10. Aliquid crystal display device comprising the liquid crystal compositionaccording to claim
 8. 11. A liquid crystal composition comprising atleast two components, at least one of which is a dioxane derivativeaccording to claim
 1. 12. A dioxane derivative represented by generalformula (I):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom, n1 and n2 are each zero, Q₁ and Q₂, each independently, are ahydrogen atom, fluorine atom or chlorine atom,

Za is a single bond and Zb represents a single bond, —CH₂CH₂—,—CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—, Y represents a hydrogenatom, a halogen atom, or a halogenated alkyl group of 1-5 carbon atoms,in which one or more not-adjacent methylene groups may be replaced by anoxygen atom or a sulfur group, in the case of Y is a fluorine atom or achlorine atom, Q1 and Q2, each independently, represent a fluorine atomor a chlorine atom, further, each element constituting the compound maybe replaced by its isotope.
 13. A dioxane derivative represented bygeneral formula (I):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom, n1 and n2, each independently, are an integer of 0-2, n1+n2=2, Q₁and Q₂, each independently, are a hydrogen atom, fluorine atom orchlorine atom,

ring A0 and A1 represent a 1,4-cyclohexylene group or a 1,4-phenylenegroup, in which 1 or more hydrogen atoms may be replaced by a fluorineatom or a chlorine atom, and one or two carbon atoms may be replaced bya silicon atom in the 1,4-cyclohexylene in, ring A0 and ring A1, Za andZb, each independently, represent a single bond, —CH₂CH₂—,—CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—, Y represents a hydrogenatom, a halogen atom, or a halogenated alkyl group of 1-5 carbon atoms,in which one or more not-adjacent methylene groups may be replaced by anoxygen atom or a sulfur group, in the case of Y is a fluorine atom or achlorine atom, Q1 and Q2, each independently, represent a fluorine atomor a chlorine atom, further, each element constituting the compound maybe replaced by its isotope.
 14. A dioxane derivative represented bygeneral formula (I):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom, n1 and n2 are each zero, Q₁ and Q₂, each independently, are ahydrogen atom, fluorine atom or chlorine atom,

and one or two carbon atoms may be replaced by a silicon atom in the1,4-cyclohexylene in A, Za is a single bond and Zb represents a singlebond, —CH₂CH₂—, —CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—, Yrepresents a hydrogen atom, a halogen atom, or a halogenated alkyl groupof 1-5 carbon atoms, in which one or more not-adjacent methylene groupsmay be replaced by an oxygen atom or a sulfur group, in the case of Zbis a single bond, at least one of Q1 and Q2 represents a fluorine atomor a chlorine atom; and in the case of Y is a fluorine atom or achlorine atom, Q₁ and Q₂, each independently, represent a fluorine atomor a chlorine atom, further, each element constituting the compound maybe replaced by its isotope.
 15. A dioxane derivative represented bygeneral formula (I):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom, n1 and n2, each independently, are an integer of 0-2, n1+n2≦2, Q1and Q2, each independently, are a hydrogen atom, fluorine atom orchlorine atom, A represents (a), (b) or (c),

ring A0 and A1 represent a 1,4-cyclohexylene group or a 1,4-phenylenegroup, in which 1 or more hydrogen atoms may be replaced by a fluorineatom or a chlorine atom, and one or two carbon atoms may be replaced bya silicon atom in the 1,4-cyclohexylene in (a), ring A0 and ring A1, Zaand Zb, each independently, represent a single bond, —CH₂CH₂—,—CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—, Y represents a hydrogenatom, a halogen atom, or a halogenated alkyl group of 1-5 carbon atoms,in which one or more not-adjacent methylene groups may be replaced by anoxygen atom or a sulfur group, in the case of n1=0 and n2=1, and A is(b), and ring A1 is 1,4-phenylene, and Za and Zb are a single bond, atleast one of Q1 and Q2 represents a fluorine atom or a chlorine atom; inthe case of Y is a fluorine atom or a chlorine atom, Q1 and Q2, eachindependently, represent a fluorine atom or a chlorine atom; and in thecase of A is (c), or Zb is —CH₂CH₂CH₂CH₂—, or n1 is not 0, Za is—CH₂CH₂CH₂CH₂—, and in the case of A is (a) and Zb is a single bond,n1+n2=1 further, each element constituting the compound may be replacedby its isotope.
 16. A dioxane derivative represented by general formula(I):

wherein R represents an alkyl group of 1-20 carbon atoms or a hydrogenatom, n1 and n2, each independently, are an integer of 0-2, n1+n2≦2, Q₁and Q₂ both are a fluorine atom, A represents (a), (b) or (c),

ring A0 and A1 represent a 1,4-cyclohexylene group or a 1,4-phenylenegroup, in which 1 or more hydrogen atoms may be replaced by a fluorineatom or a chlorine atom, and one or two carbon atoms may be replaced bya silicon atom in the 1,4-cyclohexylene in (a), ring A0 and ring A1, Zaand Zb, each independently, represent a single bond, —CH₂CH₂—,—CH₂CH₂CH₂CH₂—, OCH₂, —CH₂O—, COO— or —CF₂O—, Y represents a hydrogenatom, a halogen atom, or a halogenated alkyl group of 1-5 carbon atoms,in which one or more not-adjacent methylene groups may be replaced by anoxygen atom or a sulfur group, and in the case of A is (a) and Zb is asingle bond, n1+n2=1, further, each element constituting the compoundmay be replaced by its isotope.
 17. A liquid crystal compositioncomprising at least two components, at least one of which is a dioxanederivative according to claim
 12. 18. A liquid crystal compositioncomprising at least two components, at least one of which is a dioxanederivative according to claim
 13. 19. A liquid crystal compositioncomprising at least two components, at least one of which is a dioxanederivative according to claim
 14. 20. A liquid crystal compositioncomprising at least two components, at least one of which is a dioxanederivative according to claim
 15. 21. A liquid crystal compositioncomprising at least two components, at least one of which is a dioxanederivative according to claim 16.